TW202221153A - Method of forming metal pattern and method of manufacturing metal mask for vapor deposition - Google Patents

Abstract

Provided is a method for forming a metal pattern, said method including: a step for preparing a layered body having a negative photosensitive resin layer on a substrate; a step for radiating light from the side of the negative photosensitive resin layer that is opposite the side on which the substrate is provided, the light having a component that is obliquely incident to the thickness direction of an exposure mask, and conducting pattern exposure of the negative photosensitive resin layer via the exposure mask; a step for developing the pattern-exposed negative photosensitive resin layer and forming a resin pattern having a tapered shape; and a step for forming a metal pattern having a tapered shape corresponding to the shape of the resin pattern. Also provided is a method for manufacturing a deposition metal mask having a metal pattern obtained through the above method for forming a metal pattern.

Description

Method for forming metal pattern and method for manufacturing metal mask for vapor deposition

The present invention relates to a method for forming a metal pattern and a method for manufacturing a metal mask for vapor deposition.

In a display device (organic electroluminescence (EL) display device, liquid crystal display device, etc.) equipped with a touch panel such as an electrostatic capacitance type input device, the electrode pattern of the sensor corresponding to the visual recognition portion, the edge wiring portion, and the extraction Conductive layer patterns such as wiring in the wiring portion are provided inside the touch panel. Generally, when forming a patterned layer, the number of steps for obtaining a desired pattern shape is small, so the layer of the photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer member is separated by A method in which a mask having a desired pattern is exposed and then developed is widely used. In addition, as a method of forming a pixel of an organic EL display device, a method is known in which a metal mask (a vapor deposition mask) including a through hole is brought into close contact with a substrate for an organic EL display device, and then put into a vapor deposition device, A method of forming a pixel by vapor deposition of an organic material or the like.

Moreover, as the manufacturing method of the conventional metal mask, the thing described in Unexamined-Japanese-Patent No. 2006-152396 or Unexamined-Japanese-Patent No. 2017-226918 is known. Japanese Patent Laid-Open No. 2006-152396 describes a method for producing a metal mask, which is characterized in that, in the method for producing a metal mask based on a mask original for electroforming, a resist is applied On the first substrate of the agent, a plurality of masks having a similar transfer pattern formed in a predetermined shape are used to expose sequentially and then develop, and a predetermined shape convex portion having inclined sidewalls is formed on the first substrate. A first conductive film is formed on the entire surface of the substrate on the side where the projections of the predetermined shape are formed, metal is deposited on the upper surface of the first conductive film by electroplating, and the deposited metal is peeled off from the first conductive film to prepare A master master having predetermined-shaped recesses, on the conductive upper surface of the second substrate, a convex portion substantially identical to the predetermined-shaped protrusions based on the predetermined-shaped recesses of the master master is formed by resin on the upper surface of the second substrate. The original plate peels off the above-mentioned second substrate having the above-mentioned convex portion based on the above-mentioned resin to prepare the above-mentioned mask original plate for electroforming, and on the second conductive film exposed to the above-mentioned mask original for electroforming, by electroplating and depositing and A film of a desired metal is formed until the thickness of an opening having a side wall substantially the same as that of the inclined side wall of the recessed portion of the predetermined shape of the mask master is provided, and the metal film is peeled off from the mask master for electroforming. while making.

In Japanese Patent Laid-Open No. 2017-226918, a method for manufacturing a fine metal mask using an electroforming plating method is described. The method for manufacturing a fine metal mask includes: (a) preparing a carrier glass, and placing the carrier glass on the above-mentioned carrier glass. The step of evaporating a sacrificial layer; (b) the step of evaporating electrode metal for electroforming and electroplating to form an electrode layer; (c) the step of coating photoresist on the above-mentioned electrode layer; (e) a step of forming an electroforming plating layer on the patterned above-mentioned photoresist by electroforming plating; (f) by The step of forming a metal pattern by removing the above-mentioned photoresist; (g) the step of forming a mask pattern by forming a pattern corresponding to the above-mentioned metal pattern on the above-mentioned electrode layer; (h) In order to improve the patterned above-mentioned electrical The step of casting the electroplated layer and the above-mentioned electrode layer for rigidity and performing heat treatment; (i) the step of inspecting the above-mentioned electroformed electroplating layer and the above-mentioned mask pattern formed on the above-mentioned electrode layer; and (j) separating the above-mentioned from the above-mentioned carrier glass The steps of electroforming the electroplating layer and the above-mentioned electrode layer.

In addition, as a conventional vapor deposition mask with a substrate, the one described in Japanese Patent Laid-Open No. 2019-173181 is known. Japanese Patent Application Laid-Open No. 2019-173181 describes a vapor deposition mask with a substrate, which is characterized by comprising a glass substrate, and is formed on the substrate by electroplating and has a hole region and surrounds the hole region. A plurality of vapor deposition masks formed by the electroplating layer of the non-porous area are arranged on each of a plurality of segments and a plurality of rows.

An object to be solved by one embodiment of the present invention is to provide a method for forming a metal pattern having an excellent tapered shape. Another problem to be solved by another embodiment of the present invention is to provide a method for producing a metal mask for vapor deposition having an excellent tapered shape.

The present invention includes the following aspects. <1> A method for forming a metal pattern, comprising: A step of preparing a laminate having a negative-type photosensitive resin layer on a base material; irradiating the negative-type photosensitive resin layer from the side opposite to the side on which the base material is provided has an incident that is oblique to the thickness direction of the exposure mask The step of exposing the negative-type photosensitive resin layer through the above-mentioned exposure mask with the light of the above-mentioned composition in a pattern; step; and the step of forming a metal pattern with a conical shape corresponding to the shape of the resin pattern. <2> The method for forming a metal pattern according to <1>, wherein in the step of performing the pattern exposure, diffuse transmittances are sequentially arranged on the side opposite to the negative photosensitive resin layer side of the exposure mask. It is 5% or more of a scattering layer and an exposure light source, and scattered light is irradiated from the exposure light source through the scattering layer. <3> The method for forming a metal pattern according to <2>, wherein the scattering layer contains a black matrix material and particles existing in the black matrix material, and a difference in refractive index between the black matrix material and the particles is 0.05 above. <4> The method for forming a metal pattern according to <2> or <3>, wherein the scattering layer contains a black matrix material and particles present in the black matrix material, and the particles have an average primary particle diameter of 0.3 μm above. <5> The method for forming a metal pattern according to any one of <2> to <4>, wherein the scattering layer has irregularities on at least one surface. <6> The method for forming a metal pattern according to <5>, wherein the unevenness has a plurality of convex portions, and the distance between the adjacent convex portions and the tops of the convex portions is 10 μm to 50 μm. <7> The method for forming a metal pattern according to any one of <2> to <6>, wherein the scattering layer and the exposure mask are arranged at positions not in contact with each other. <8> The method for forming a metal pattern according to any one of <2> to <6>, wherein the scattering layer is in contact with the exposure mask, and the negative photosensitive resin is in the exposure mask It is arranged on the side opposite to the layer side. <9> The method for forming a metal pattern according to any one of <2> to <6>, wherein the exposure mask has the scattering layer formed on the surface opposite to the surface on which the light shielding pattern is formed The diffuse exposure mask. <10> The method for forming a metal pattern according to any one of <1> to <9>, wherein the step of preparing includes using a negative photosensitive resin having a dummy support and arranged on the dummy support The transfer material of the layer is a step of transferring the negative photosensitive resin layer contained in the transfer material onto the base material to form the layered product. <11> The method for forming a metal pattern according to <10>, wherein the pattern exposure in the pattern exposure step is contact exposure in which the dummy support is brought into contact with the exposure mask to perform exposure. <12> The method for forming a metal pattern according to <10>, wherein the pattern exposure in the pattern exposure step is performed by peeling off the dummy support, and then making the exposure mask and the negative-type photosensitivity. The above-mentioned laminated body of the resin layer is contacted to perform contact exposure for exposure. <13> The method for forming a metal pattern according to any one of <1> to <12>, wherein the base material is a conductive base material. <14> The method for forming a metal pattern according to any one of <1> to <13>, wherein the metal pattern is a metal pattern formed by an electroplating method. <15> The method for forming a metal pattern according to any one of <1> to <14>, further comprising a step of removing the resin pattern after the step of forming the metal pattern. <16> The method for forming a metal pattern according to <15>, wherein the resin pattern is removed with a chemical solution. <17> The method for forming a metal pattern according to any one of <1> to <16>, further comprising a step of removing the base material from the metal pattern. <18> The method for forming a metal pattern according to any one of <1> to <17>, wherein the resin pattern includes a truncated pyramid shape or a truncated cone shape resin pattern. <19> The method for forming a metal pattern according to any one of <1> to <18>, wherein the negative photosensitive resin layer has a thickness of 10 μm or more. <20> The method for forming a metal pattern according to any one of <1> to <19>, wherein the obtained metal pattern is a metal pattern for a metal mask for vapor deposition. <21> A method for producing a metal mask for vapor deposition, comprising the step of forming a metal pattern by the method for forming a metal pattern according to any one of <1> to <20>. [Inventive effect]

According to one embodiment of the present invention, it is possible to provide a method of forming a metal pattern having an excellent tapered shape. According to another embodiment of this invention, the manufacturing method of the metal mask for vapor deposition which is excellent in a tapered shape can be provided.

Hereinafter, the content of the present invention will be described. In addition, although it demonstrates referring drawings, a code|symbol may be abbreviate|omitted. In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In addition, in this specification, "(meth)acrylic acid" means both or either of acrylic acid and methacrylic acid, and "(meth)acrylate" means both or either of acrylate and methacrylate . Furthermore, in the present invention, when there are plural substances corresponding to each component in the composition, unless otherwise specified, the amount of each component in the composition refers to the corresponding plural substances present in the composition. total amount. In this specification, the term "step" includes not only an independent step, but also in the case where it cannot be clearly distinguished from other steps, as long as the intended function of the step is exerted, it is also included in the term. In the notation of groups (atomic groups) in the present specification, the notation that is not substituted and unsubstituted includes a group without a substituent and a group with a substituent. For example, "alkyl" is meant to include not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure by light but also drawing by particle beams such as electron beams and ion beams. In addition, as the light used for exposure, the bright line spectrum of a mercury lamp, and actinic rays (active energy rays such as extreme ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams) are generally mentioned. ). In addition, the chemical structural formula in this specification may be described as a simplified structural formula in which a hydrogen atom is omitted. In the present invention, "mass %" and "weight %" have the same meaning, and "mass part" and "weight part" have the same meaning. Moreover, in this invention, the combination of 2 or more of preferable aspects is a more preferable aspect. In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention, unless otherwise specified, are molecular weights obtained by using TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL ( Both are product names manufactured by TOSOH CORPORATION) column gel permeation chromatography (GPC) analysis equipment, using solvent THF (tetrahydrofuran), differential refractometer for detection, and using polystyrene as a standard material for conversion and obtained molecular weight.

(Method of forming metal pattern) The method for forming a metal pattern of the present invention includes the steps of preparing a laminate having a negative-type photosensitive resin layer on a base material; and irradiating the negative-type photosensitive resin layer from the side opposite to the side on which the base material is provided. The step of subjecting the negative photosensitive resin layer to pattern exposure with light having a component obliquely incident in the thickness direction of the exposure mask through the exposure mask; developing the negative photosensitive resin layer exposed in the pattern And the step of forming a resin pattern with a tapered shape; and the step of forming a metal pattern with a tapered shape corresponding to the shape of the resin pattern.

In the conventional method of forming a metal pattern, the metal pattern can be formed by forming a through hole in a metal plate by an etching method using a photolithography technique. For example, after patterning a photoresist on a stainless steel (SUS) substrate having a thickness of 100 μm to 200 μm, the SUS substrate is etched into the shape of the opening to be realized using an etching solution. However, in the method of processing a metal plate by etching with a chemical solution, not only in the thickness direction but also in the surface direction of the metal plate is etched to generate so-called side etching, so there are problems with the dimensional accuracy and stability of the processing. Therefore, as a processing method for producing a high-precision metal mask, a method for producing a fine metal mask using an electroforming plating method has been proposed. As an example of a method of manufacturing a metal mask by electroforming, first, on one surface of a base substrate made of a nonconductive material such as glass, a metal coating (ie, a conductive film) is formed by sputtering or the like to Conductivity is imparted, and a high-precision, photoresist-based mask is transcribed on the conductive film to form an aperture pattern. Next, on the conductive film exposed from the photoresist, a power source is connected to the conductive film in a plating solution, and nickel or a nickel alloy is deposited to a desired thickness. Finally, the deposited metal film is peeled off to serve as a metal mask. At this time, in order to produce a metal mask having a taper-shaped opening, the pattern of the photoresist needs to be a pattern having an inclined tapered shape on the sidewall.

In this way, the present inventors found that in the conventional metal pattern forming method, there is a problem in the tapered shape. In the method for forming a metal pattern of the present invention, light having a component that is obliquely incident in the thickness direction of the exposure mask is irradiated from the side opposite to the side on which the base material is provided in the negative photosensitive resin layer. By subjecting the above-mentioned negative-type photosensitive resin layer to pattern exposure, the exposure amount, especially the exposure amount of the side portion of the formed resin pattern, is reduced according to the length in the thickness direction of the above-mentioned negative-type photosensitive resin layer. produces a conical shape. Furthermore, according to the above aspect, the tapered shape of the resin pattern and the tapered shape of the obtained metal pattern can be sufficiently controlled. Therefore, it is presumed that a metal pattern having an excellent tapered shape can be obtained.

The metal pattern produced by the method for forming a metal pattern of the present invention is a metal pattern having an inverted tapered shape or a forward tapered shape when it is inverted. For example, it can be suitably used as a metal mask for vapor deposition, or more appropriately It can be used as an FMM (Fine Metal Mask: fine metal mask) for organic EL display device manufacture, and can be used as an FMM for organic light emitting diode (OLED) manufacture especially suitably.

In addition, FIG. 1 shows the schematic diagram which shows a preferable example of the formation method of the metal pattern of this invention. FIG. 1 is composed of FIGS. 1( a ) to 1 ( e ) corresponding to the stages of the respective steps. 1( a ) to 1 ( e ) show a schematic cross-sectional view of a cross-section in a direction perpendicular to the surface direction of the base material in a part of the formed metal pattern. As shown in FIG.1(a), in the process of preparing the said laminated body, the laminated body 100 which has the negative photosensitive resin layer 104a on the base material 102 is prepared. The negative-type photosensitive resin layer 104a in the layered body 100 is exposed to light having a component obliquely incident in the thickness direction of the exposure mask (not shown) from the side opposite to the side on which the base material 102 is provided. The photosensitive resin layer 104a is subjected to pattern exposure and further developed to form a resin pattern 104 having a tapered shape as shown in FIG. 1( b ). Next, as shown in FIG. 1( c ), a metal pattern 106 having an inverted tapered shape corresponding to the shape of the resin pattern 104 described above is formed by a plating method or the like. In addition, the taper angle of the resin pattern is θ1, and the taper angle of the metal pattern is θ2. Not only in FIG. 1( c ), but also θ1 and θ2 are the same in FIG. 1( b ), FIG. 1( d ), and FIG. 1( e ). The resin pattern 104 is removed from the base material 102 having the resin pattern 104 and the metal pattern 106 by using a chemical solution or the like to obtain the base material 102 having the metal pattern 106 as shown in FIG. 1( d ). Substrate 102 may be further removed from substrate 102 having metal pattern 106 . Only the metal pattern 106 can be obtained as shown in FIG. 1( e ) by removing the base material 102 . In addition, when removing the base material 102 as shown in FIG.1(e), it is preferable that the metal pattern 106 is the pattern which connects all the parts of each metal part which are not shown in figure.

<Preparation steps> The formation method of the metal pattern of this invention includes the process (it is also called "preparation process") of preparing the laminated body which has a negative photosensitive resin layer on a base material. In addition, the above-mentioned preparation step includes using a transfer material having a dummy support and a negative-type photosensitive resin layer disposed on the dummy support, and transferring the negative-type photosensitive resin layer included in the transfer material to the above-mentioned transfer material. Preferably, the step of forming the above-mentioned layered body is performed on the substrate. The negative photosensitive resin layer and the transfer material having the negative photosensitive resin layer used in the present invention will be described later. The above-mentioned laminate system has at least a laminate of a base material and a negative-type photosensitive resin layer, and may have other layers such as a dummy support and a release layer, but the laminate of the base material, the negative-type photosensitive resin layer and the dummy support, Or the laminated body which consists of a base material and a negative photosensitive resin layer is preferable, and the laminated body which consists of a base material, a negative photosensitive resin layer, and a dummy support body is more preferable. The thickness of the negative-type photosensitive resin layer is not particularly limited, and can be appropriately set according to the desired thickness of the resin pattern described later, from the viewpoint of the taper angle and dimensional stability of the obtained metal pattern. , 8 μm or more is preferred, 10 μm or more is more preferred, 15 μm or more is further preferred, 20 μm or more is particularly preferred, and 30 μm or more is the best. Moreover, it is preferable that the upper limit of the thickness of the said negative photosensitive resin layer is 100 micrometers or less.

-Substrate- The above-mentioned base material is preferably a plate-shaped base material, and more preferably a metal substrate. In addition, the above-mentioned base material is preferably a conductive base material, that is, a conductive base material having electrical conductivity at least on its surface, and the above-mentioned base material is a base material composed of a conductive material, that is, the whole base material has electrical conductivity. The conductive substrate is better. As the base material, for example, a thin plate made of a metal such as stainless steel, or a conductive film of nickel formed on the upper surface of glass serving as an insulating material by electrolytic plating can be appropriately used. As said glass, an alkali-free glass or a soda glass can be used suitably. As a conductive material used for the said base material, nickel, chromium, tantalum, tungsten, indium tin oxide (ITO), etc. can be used, for example. In addition, when imparting conductivity to the base material, formation of a conductive film by electroless plating and physical methods such as sputtering, vacuum deposition, and ion plating can also be used. Furthermore, as a material which becomes the base material of a base, a glass plate, a stainless steel plate, a silicon substrate, etc. are mentioned. In the case of using a substrate having a conductive layer on the surface, the thickness of the conductive layer is preferably thin as long as it has the conductivity required for electrolytic plating treatment. Moreover, it is preferable that the thickness of the said electroconductive layer is 0.5 micrometer - 5 micrometers specifically, for example.

The method for producing the above-mentioned layered product is not particularly limited. For example, a method of forming a negative-type photosensitive resin layer on a substrate using a transfer material, and coating and drying a negative-type photosensitive resin composition on the substrate can be mentioned. The method of material, etc., the method of bonding the negative photosensitive resin layer in a transfer material to a base material is mentioned suitably. Moreover, when the said transfer material has a dummy support body, it is preferable to peel it after the said bonding. Furthermore, when the said transfer material has a coverlay film, after removing a coverlay film from the surface of a negative photosensitive resin layer, what is necessary is just to bond.

There is no restriction|limiting in particular as a method of bonding a base material and a transcription|transfer material (negative photosensitive resin layer in a transcription|transfer material), A well-known transcription|transfer method and a lamination method can be used. The above-mentioned bonding is preferably performed by stacking the base material on the negative photosensitive resin layer side in the transfer material, and applying pressure and heating using a mechanism such as a roller. Moreover, when performing the said bonding, well-known laminators, such as a laminator, a vacuum laminator, and an automatic cutting laminator which can further improve productivity, can be used.

Furthermore, it is preferable to carry out the said bonding by a roll-to-roll method. Hereinafter, the roll-to-roll method will be described. In the present invention, the roll-to-roll method refers to a method including a step of using a substrate capable of winding and unwinding as the substrate, and unwinding at least one of the substrate and the transfer material (also referred to as "unwinding step".) and the step of winding the above-mentioned laminate (also referred to as "winding step".), and in at least one step (preferably all steps, or all steps except the heating step) The base material and the transfer material are bonded together while conveying at least one of the base material and the transfer material and the above-mentioned layered product. The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and a known method may be used in the manufacturing method using the roll-to-roll method.

<Pattern exposure step> The method for forming a metal pattern of the present invention includes irradiating light having a component obliquely incident in the thickness direction of the exposure mask from the side opposite to the side on which the base material is provided in the negative photosensitive resin layer, and interposing the exposure through the exposure The mask exposes the negative-type photosensitive resin layer in a pattern (also referred to as a "pattern exposure step"). The method of irradiating light having a component obliquely incident in the thickness direction of the exposure mask is not particularly limited, and examples include a method of irradiating the exposure mask with scattered light, and irradiating light with a wide irradiation angle using optical members such as lenses. To the method of exposure mask, etc. The method of forming the scattered light is not particularly limited, and a known method can be used. For example, a method of forming the scattered light by a scattering layer can be appropriately mentioned. There is no particular limitation on the method of forming light with a wide irradiation angle, and a known method can be used. For example, light irradiated from an LED (light emitting diode) with a narrow irradiation angle can be transmitted through a wide-angle lens or a fisheye lens. In order to make the irradiation angle a wide-angle method. In the pattern exposure step, scattered light is irradiated to the exposure mask from the side opposite to the side where the base material is provided in the negative-type photosensitive resin layer, and the negative-type photosensitive resin layer is irradiated with light by transmitting the light of the exposure mask. The photosensitive resin layer is preferably subjected to pattern exposure. Specifically, as a pattern exposure step, for example, an exposure light source arranged from the side opposite to the negative-type photosensitive resin layer side of the above-mentioned exposure mask can be preferably mentioned, The photosensitive resin layer is irradiated with scattered light to perform the step of pattern exposure. Irradiation of scattered light is performed by arranging a scattering layer with a diffuse transmittance of 5% or more and an exposure light source in this order on the side opposite to the negative photosensitive resin layer side of the exposure mask, and irradiating the scattered light from the exposure light source through the scattering layer Light is better. In addition, the pattern exposure in this invention means the form of pattern exposure, ie, the exposure of the form which exists in an exposure part and a non-exposed part in a negative photosensitive resin layer.

In the pattern exposure step, the detailed arrangement and specific size of the pattern in the above-described pattern exposure are not particularly limited. For example, it only needs to be appropriately selected according to the manufactured display device (eg, a touch panel). In addition, in the above-mentioned pattern exposure, as the above-mentioned exposure mask, a mask (light-shielding mask) for exposing to a desired shape is used. It does not specifically limit as said exposure mask, The mask of a well-known material can be used.

-Exposure light source- As the exposure light source in the present invention, a known one can be used. The exposure light source can be appropriately selected and used as long as it is a light source that irradiates light of a wavelength capable of exposing the negative photosensitive resin layer (for example, 365 nm or 405 nm). Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode) can be mentioned. The light during the exposure is not particularly limited as long as it can expose the negative photosensitive resin layer, and it is preferable to include light with a wavelength of 365 nm or 405 nm, more preferably, light with a wavelength of 365 nm, and light with a wavelength of 365 nm is Excellent. The exposure amount is not particularly limited as long as the negative-type photosensitive resin layer can be exposed, but is preferably 5mJ/cm ² to 1,000mJ/cm ² , and more preferably 10mJ/cm ² to 500mJ/cm ² .

In the case of using a transfer material having a dummy support and a negative-type photosensitive resin layer disposed on the dummy support, in the pattern exposure step, the dummy support may be peeled off from the negative-type photosensitive resin layer. After exposure, the dummy support may be peeled off after exposure through the dummy support. With regard to the peeling of the dummy support, for example, the dummy support and the dummy support can be stretched while conveying the laminate including the negative photosensitive resin layer and the dummy support at a speed of 0.5 m/min to 4.0 m/min. The angle formed by the layered body is 10° to 180°. By peeling off the dummy support before exposure, foreign matter contained in the dummy support or foreign matter attached to the dummy support can be prevented from adversely affecting exposure. In order to prevent contamination of the negative-type photosensitive resin layer due to contact between the negative-type photosensitive resin layer and the exposure mask, and to avoid the influence on exposure caused by foreign matter adhering to the exposure mask, exposure through a dummy support is performed as better. That is, a dummy support is provided on the negative photosensitive resin layer in the laminate, and the exposure in the step of forming the resin pattern is preferably performed through the dummy support, and the pattern exposure is preferably performed. The above-mentioned pattern exposure in the step of making the above-mentioned dummy support body and the above-mentioned exposure mask to contact for exposure is better. Moreover, after the above-mentioned pattern exposure in the above-mentioned pattern exposure step is to peel off the above-mentioned dummy support, it is also preferable that the above-mentioned exposure mask is brought into contact with the above-mentioned laminated body having the above-mentioned negative-type photosensitive resin layer for exposure. . As an exposure method using an exposure mask, a known high-definition exposure mechanism such as mask close exposure, proximity exposure, or projection exposure using a photolithography machine can be used. In the case of using a photolithography machine for exposure, the distance between the exposure mask and the negative photosensitive resin layer (exposure proximity gap) can be arbitrarily set. 200 μm is particularly preferred. Also, as the exposure mask, a binary mask, a gray mask, a halftone mask, or the like can be used.

-scattering layer- In the pattern exposure step, through a scattering layer (more preferably, a scattering layer having a diffuse transmittance of 5% or more) disposed between the exposure light source and the exposure mask, a component having a component that is incident obliquely in the thickness direction of the exposure mask is subjected to Irradiation of light (preferably scattered light) is preferred. The scattering layer may be provided alone, or other layers of the laminate, such as a base material of an exposure mask, a dummy support in a dry film resist, and other materials having scattering properties may be used to impart a function as a scattering layer. From the viewpoint of the taper angle of the obtained resin pattern and metal pattern, the scattering layer and the exposure mask are preferably arranged at positions not in contact with each other. The distance between the said scattering layer and the said exposure mask should just be 0 micrometer - 200 micrometers, for example. Moreover, it is preferable to arrange|position the said scattering layer on the side opposite to the said negative photosensitive resin layer side in the said exposure mask from the viewpoint of the taper angle of the resin pattern and metal pattern obtained. The measurement of diffuse transmittance uses the index of light diffuse transmittance. The light diffusion transmittance refers to the transmittance of the diffused light of the parallel component removed from the total transmittance of all the light rays including the parallel component and the diffused component in the light transmitted through the scattering layer when light is irradiated on the scattering layer. The light-diffusing transmittance can be calculated|required based on JIS K 7136 "The calculation method of the haze of a plastic-transparent material (2000)." That is, the haze value (haze value) refers to a value represented by the following formula, and thus the diffuse transmittance of the scattering layer serving as the subject can be obtained by using a haze meter. Haze value (Haze value)%=[Diffuse transmittance (Td)/Total transmittance (Tt)]×100 As a measuring apparatus in this invention, the value using the haze meter NDH7000II of NIPPON DENSHOKU INDUSTRIES Co., LTD was used.

The diffuse transmittance of the scattering layer is preferably 5% or more, more preferably 50% or more, further preferably 70% or more, and particularly preferably 90% or more. The upper limit of the diffuse transmittance is not particularly limited, and can be, for example, 100%.

The scattering angle of the scattering layer is preferably 15° or more, more preferably 20° or more, further preferably 20° or more and 80° or less, and particularly preferably 40° or more and 70° or less. Here, the scattering angle refers to the width (the sum of the positive side and the negative side) when the vertical direction of the light transmitted through the scattering layer is taken as the angle of 0° of the intensity and 1/2 of the intensity. It is also sometimes expressed in terms such as full angle at half maximum. The scattering angle can be measured using a goniometer or the like. The light scattering characteristic is generally symmetrical on the positive side and the negative side, and when the positive side and the negative side are asymmetrical, the definition of the scattering angle does not change. When the value of the scattering angle differs depending on the orientation of the measurement surface, the largest value among them is set as the scattering angle of the scattering layer.

The scattering layer is not particularly limited, but from the viewpoint of easy adjustment of the diffuse transmittance and easy availability, the scattering layer is a scattering layer containing a black matrix material and particles present in the black matrix material (hereinafter, sometimes referred to as containing a black matrix material). and particle scattering layer) or a scattering layer having concavities and convexities on at least one surface is preferable.

-scattering layer containing black matrix material and particles- An aspect of the scattering layer used in the present invention includes a black matrix material and particles (hereinafter, sometimes referred to as specific particles) that are present in the black matrix material and that impart light scattering properties to the scattering layer. layer. The scattering layer containing specific particles is preferably a layer containing specific particles dispersed in a transparent black matrix material. As a black matrix material, glass, quartz, resin material, etc. are mentioned. When glass or quartz is used as the black matrix material, specific particles may be kneaded to be uniformly dispersed in the glass or quartz and used as a scattering layer. When a resin material is used as the black matrix material, a resin capable of forming an ultraviolet-transmitting resin layer is preferable, and examples thereof include acrylic resin, polycarbonate resin, polyester resin, polyethylene resin, and polypropylene resin. , epoxy resin, urethane resin, silicone resin, etc. When a resin material is used as the black matrix material, the scattering layer can be formed by a known method. For example, a plate-shaped scattering layer can be obtained by melt-kneading resin particles and specific particles of the black matrix material and by injection molding. In addition, the scattering layer may be formed by curing a resin composition containing a resin precursor monomer and specific particles, or the resin composition containing specific particles may be cured and kneaded in a mixture containing a resin material and a solvent that is an optional component. object as the scattering layer. In addition, the formation method of a scattering layer is not limited to the above-mentioned method.

Specific Particles In order to impart sufficient light-scattering properties to the scattering layer, the scattering layer contains a black matrix material and particles present in the black matrix material, and the difference in refractive index between the black matrix material and the particles is preferably 0.05 or more, preferably 0.05 -1.0 is more preferable, and 0.05-0.6 is more preferable. When the difference in refractive index between the black matrix material and the specific particles is within the above range, the scattered light intensity can be greatly increased, and when the scattered light intensity is too large, the energy imparted by the reflection of incident light becoming too large, which is a concern, is reduced. While being suppressed, it is possible to impart sufficient energy to harden the negative photosensitive resin layer.

The specific particles include a black matrix material and particles present in the black matrix material in order to impart sufficient light scattering properties to the scattering layer, and the average primary particle diameter of the particles is preferably 0.3 μm or more. The average primary particle size of the specific particles is more preferably in the range of 0.3 μm to 2.0 μm, and particularly preferably in the range of 0.5 μm to 1.5 μm. When the average primary particle size is within the above range, Mie scattering of ultraviolet rays occurs, the intensity of forward scattered light increases, and it becomes easy to impart sufficient energy to harden the negative photosensitive resin layer. The average primary particle diameter of specific particles is calculated by measuring the particle diameters of any 200 specific particles existing within a viewing angle using an electron microscope, and by arithmetically averaging the measured values. In addition, when the shape of the particle is not spherical, the longest side is used as the particle diameter.

Specific particles include, for example, zirconia particles (ZrO ₂ particles), niobium oxide particles (Nb ₂ O ₅ particles), titanium oxide particles (TiO ₂ particles), alumina particles (Al ₂ O ₃ particles), and Inorganic particles such as silicon oxide particles (SiO ₂ particles), and organic particles such as cross-linked polymethyl methacrylate.

The scattering layer may contain only one type of specific particles, or may contain two or more types. The content of the specific particles is not particularly limited, and it is preferable to achieve a desired diffuse transmittance or a desired scattering angle by adjusting the type, size, content, shape, refractive index, etc. of the specific particles in the scattering layer. As content of a specific particle, for example, it can be set to 5 mass % - 50 mass % with respect to the total mass of a scattering layer.

-Diffuser layer with unevenness on at least one surface- Another aspect of the scattering layer includes a scattering layer having irregularities on at least one surface. By having unevenness on at least one surface of the scattering layer, light is scattered by the unevenness, and the scattered light is irradiated to the negative photosensitive resin layer through the scattering layer. Regarding the unevenness in the scattering layer, the distance between the adjacent convex portions and the tops of the convex portions is preferably 10 μm to 50 μm. As for the concavities and convexities, the adjacent convex portions and the bottoms of the convex portions are in contact with each other, and from the viewpoint of light scattering, it is preferable that the adjacent convex portions and the convex portions are densely formed without voids at equal intervals. A desired diffuse transmittance or a desired scattering angle can be realized by adjusting the size and shape of the convex portion, the formation density per unit area of the convex portion, and the like. The shape of the convex portion is not particularly limited, and can be appropriately selected from hemispherical, conical, pyramidal, ridged, and the like in accordance with the target diffusion transmittance, diffusion angle, and the like.

A commercial item can be used for the scattering layer which has unevenness|corrugation on at least one surface. Examples of commercially available products include Optical SOLUTIONS Corporation, lens diffuser (registered trademark), product name: (hereinafter, the same) LSD5ACUVT10, LSD10ACUVT10, LSD20ACUVT10, LSD30ACUVT10, LSD40ACUVT10, LSD60ACUVT10, LSD80ACUVT10 (the above are UV-transmitting acrylic resin), Lens diffuser (registered trademark): LSD5AC10, LSD10AC10, LSD20AC10, LSD30AC10, LSD40AC10, LSD60AC10, LSD80AC10 (the above are made of acrylic resin), Lens diffuser (registered trademark): LSD5PC10, LSD10PC10, LSD20PC10, LSD30PC10, LSD40PC10, LSD60PC10, LSD80PC10, LSD60×10PC10, LSD60×1PC10, LSD40×1PC10, LSD30×5PC10 (the above are polycarbonate), Lens diffuser (registered trademark): LSD5U3PS (the above is made of quartz glass), etc.

Other scattering layers include Fly eye lens FE10 manufactured by Nihon Tokushu Kogaku Jushi Co., Ltd., Diffuser manufactured by FIT Corporation, SDXK-1FS manufactured by SUNTECHOPT Corporation, SDXK-AFS, SDXK-2FS, Fillplus, Inc. Manufactured light diffusing film MX, acrylic diffusing sheet manufactured by SHIBUYA OPTICAL CO.,LTD ADF901, ADF852, ADF803, ADF754, ADF705, ADF656, ADF607, ADF558, ADF509, ADF451, Nano manufactured by Oji F-Tex Co., Ltd. Buckling (registered trademark), light diffusing films HDA060, HAA120, GBA110, DCB200, FCB200, IKA130, EDB200, 3M Japan Limited made Scotch Cal (registered trademark) light diffusing films 3635-30, 3635-70 manufactured by LINTEC Corporation, Light up (registered trademark) SDW, EKW, K2S, LDS, PBU, GM7, SXE, MXE, SP6F, Opt Saver (registered trademark) L-9, L-11, L-19, manufactured by KIMOTO CO., LTD. L-20, L-35, L-52, L-57, STC3, STE3, Chemical Matte (registered trademark) 75PWX, 125PW, 75PBA, 75BLB, 75PBB, Opulse (registered trademark) PBS-689G manufactured by KEIWA Inc., PBS-680G, PBS-689HF, PBS-680HG, PBS-670G, UDD-147D2, UDD-148D2, SHBS-227C1, SHBS-228C2, UDD-247D2, PBS-630L, PBS-630A, PBS-632A, BS- 539, BS-530, BS-531, BS-910, BS-911, BS-912, Legend (registered trademark) manufactured by Kuraray Co., Ltd. PC, CL, HC, OC, TR, MC, SQ, EL , OE, TSUJIDEN CO., LTD. D120P, D121UPZ, D121UP, D261SIIIJ1, D261IVJ1, D263SIII, S263SIV, D171, D171S, D174S and so on.

The thickness of the scattering layer is preferably 2 mm or less, more preferably 1 mm or less, and even more preferably 100 μm or less. The thickness of the scattering layer is preferably 0.5 μm or more, and more preferably 1 μm or more. As the thickness of the scattering layer, the arithmetic mean value of the measurement values at arbitrary 5 places measured by observing the cross section of the scattering layer with a scanning electron microscope (SEM) was adopted.

The irradiation of scattered light is not limited to the irradiation of light through a separate scattering layer. For example, as the layers other than the light shielding portion in the exposure mask, an exposure mask having light-scattering properties can be appropriately used. When a diffusing exposure mask (also simply referred to as a "diffusing exposure mask") is used, the light passing through the exposure mask becomes scattered light. Among them, from the viewpoint of the taper angle of the obtained resin pattern and metal pattern, a preferred example is an aspect in which the above-mentioned exposure mask forms the above-mentioned scattering on the surface opposite to the surface on which the light-shielding pattern is formed. The diffuse exposure mask of the layer.

In the irradiation of scattered light in the pattern exposure step, the arrangement position of the scattering layer is not particularly limited as long as it is between the exposure light source and the exposure mask. For example, an exposure mask, a scattering layer, and an exposure light source may be provided in this order on the side opposite to the side on which the base material is provided in the negative photosensitive resin layer.

An example of the arrangement position of the scattering layer when irradiating scattered light (a preferred example of light having a component obliquely incident in the thickness direction of the exposure mask) through the scattering layer will be described with reference to the drawings. 2 is a schematic cross-sectional view showing a first aspect of an arrangement position of a scattering layer in light irradiation in a pattern exposure step. The exposed laminate precursor shown in FIG. 2 has a substrate 12, a negative photosensitive resin layer 16, a polyethylene terephthalate (PET) film serving as a dummy support 24, and an exposure having a light-shielding region 26A The mask 26 and the scattering layer 28 are arranged on the side of the exposure light source (not shown) (the side opposite to the side where the substrate 12 is provided in the negative photosensitive resin layer 16 ), and are arranged at a position not in contact with the exposure mask 26 . In FIGS. 2 to 4 , the optical paths of the irradiation light are schematically indicated by arrows. As described in FIG. 2 , the scattered light transmitted through the scattering layer 28 and scattered is scattered at an angle with the normal direction of the negative photosensitive resin layer 16 . Therefore, curing in the negative photosensitive resin layer 16 is difficult. The side surface of the patterned hardened layer 16A formed in the region has a gentle slope with respect to the surface direction of the base material. The taper angle of the side surface of the patterned hardened layer 16A with respect to the surface direction of the base material is preferably 50° or less.

3 is a schematic cross-sectional view showing a second aspect of the arrangement position of the scattering layer in the light irradiation in the pattern exposure step. The exposed laminate precursor in FIG. 3 has the same layer structure as the exposed laminate precursor shown in FIG. 2 . In the second aspect shown in FIG. 3 , the scattering layer 28 is arranged in contact with the exposure mask 26 . The scattering layer 28 may be integrally formed on the surface of the exposure mask 26 on the light source side by coating, sticking, or the like. In the second aspect shown in FIG. 3 , the scattered light transmitted through the scattering layer 28 and scattered by the light-shielding region 26A without the exposure mask 26 is incident as scattered light as scattered light, as shown in FIG. 3 , when viewed from the side In the case of the patterned cured layer 16A formed in the cured region in the negative photosensitive resin layer 16, it has a gentle slope with respect to the surface direction of the base material. The patterned hardened layer 16A preferably has a taper angle of 50° or less with respect to the surface direction of the base material in a cross section parallel to the normal line direction of the base material.

4 is a schematic cross-sectional view showing an example of an example of a scattering exposure mask of a third aspect used as an arrangement position of a scattering layer in light irradiation in a pattern exposure step. In the third aspect shown in FIG. 4 , as the exposure mask, a scattering exposure mask 32 having a diffuse transmittance of 5% or more is used. The scattering exposure mask 32 is a scattering exposure mask 32 having a light-shielding region 32A in a desired region of the scattering base material. The diffuse transmittance of the diffuse exposure mask is as described above. In the third aspect shown in FIG. 4 , the irradiated light irradiated by the exposure light source (not shown) disposed on the side opposite to the side where the substrate 12 is provided in the negative photosensitive resin layer 16 is transmitted and scattered The mask 32 is naturally exposed to scattered scattered light, and since it enters the negative photosensitive resin layer 16 at an angle with respect to the normal direction of the substrate, as shown in FIG. In the case of the pattern-like hardened layer 16A formed in the hardened region in the resin layer 16, it has a gentle slope with respect to the surface direction of the base material. The patterned hardened layer 16A preferably has a taper angle of 50° or less with respect to the surface direction of the base material in a cross section parallel to the normal line direction of the base material.

In any aspect, in the method for forming a metal pattern of the present invention, scattered light is irradiated from the exposure light source to the exposure mask, and the negative photosensitive resin layer is exposed in a pattern through the exposure mask. Therefore, the side surface portion of the patterned hardened layer formed in the hardened region in the negative photosensitive resin layer has a gentle slope with respect to the surface direction of the base material, and is unlikely to become a side surface with a steep slope, so that the various advantages described above can be formed. layered body. In order to improve the flatness of the pattern after exposure, it is also preferable to perform heat treatment before the step of forming the resin pattern. By the process called PEB (Post Exposure Bake: Post Exposure Bake), it is possible to reduce the roughness of the pattern edge caused by the standing wave generated in the negative photosensitive resin layer at the time of exposure.

<resin pattern forming step> The method of forming a metal pattern of the present invention includes a step of developing the above-mentioned negative photosensitive resin layer exposed to the above-mentioned pattern to form a resin pattern having a tapered shape (also referred to as "resin pattern forming step"). The thickness of the formed resin pattern can be appropriately selected from the relationship between the hole pitch, the opening diameter, and the vapor deposition angle, but from the viewpoints of the taper angle and dimensional stability of the obtained metal pattern, 10 μm or more is preferable. 15 μm or more is more preferable, 20 μm or more is further preferable, and 30 μm or more is particularly preferable. In addition, the upper limit is preferably 100 μm or less. In the present invention, the resin pattern, the metal pattern, and the thickness of each layer are measured by observing a transfer material or a cross section in a direction perpendicular to the surface direction of the laminate by a scanning electron microscope (SEM). . In addition, unless otherwise specified, the value of the said thickness is the average value of the thickness of 10 or more measurement places.

In the present invention, the "tapered shape" in the resin pattern refers to the measurement of the width (W1) of the top (the side opposite to the substrate side) of the resin pattern and the width (W1) of the bottom (the substrate side) of the resin pattern. W2), the relationship of W1<W2 is established. The taper angle refers to the angle formed by the side of the pattern and the substrate, and can be approximated to the angle formed by the above-mentioned straight line and the substrate surface when a straight line connects the end of the top and the end of the bottom of the resin pattern. The taper angle can also be appropriately selected from the relationship between hole spacing, opening diameter, and vapor deposition angle, preferably 10° to 80°, more preferably 20° to 70°, and particularly preferably 30° to 60°. In addition, the tapered shape of the resin pattern in the present invention is preferably a forward tapered shape with respect to the tapered shape of the base material.

In the present invention, the angle of the tapered shape of the resin pattern can be adjusted, for example, by selecting the angle and the amount of the light in the component obliquely incident on the exposure mask. For example, when a scattering layer is used, adjustment of the scattering angle and diffuse transmittance of the scattering layer, and the light quantity of the exposure light source, etc. are mentioned.

The shape of the resin pattern is not particularly limited and may be appropriately selected according to needs, but from the viewpoint of further exerting the effects of the present invention, the resin pattern preferably includes a frustum-shaped resin pattern, including a frustum-shaped resin pattern. Or a truncated cone-shaped resin pattern is more preferable. In addition, from the viewpoint of further exerting the effects of the present invention, it is preferable that the resin pattern includes a resin pattern with a maximum diameter of 100 μm or less on the surface opposite to the substrate side, including the resin pattern on the opposite side to the substrate side. Resin patterns with a maximum diameter of a surface of 50 μm or less are more preferable, and a resin pattern with a maximum diameter of 0.1 μm or more and 20 μm or less, including the side opposite to the base material side, is more preferable, including the side opposite to the base material side. The resin pattern in which the maximum diameter of the surface is 0.2 μm or more and 10 μm or less is particularly preferred. Furthermore, from the viewpoint of further exerting the effects of the present invention, the resin pattern is preferably a resin pattern having an area of 1,200 μm ² or less on the surface opposite to the substrate side including the opposite side to the substrate side. Resin patterns with a surface area of 500 μm ² or less are more preferred, and resin patterns with an area of 0.1 μm ² or more and 250 μm ² or less including the substrate side are more preferred, including the opposite side of the substrate side. A resin pattern having an area of one side surface of 1 μm ² or more and 100 μm ² or less is particularly preferred.

In the above-mentioned resin pattern forming step, a resin pattern having a tapered shape is formed by developing the pattern-exposed negative photosensitive resin layer. When the said transfer material has an intermediate layer, in a resin pattern formation process, the intermediate layer of a non-exposed part is also removed together with the negative photosensitive resin layer of a non-exposed part. In addition, in the resin pattern forming step, the intermediate layer of the exposed portion may be removed by dissolving or dispersing in a developing solution.

The development of the exposed negative-type photosensitive resin layer in the above-mentioned resin pattern forming step can be performed using a developer. The developer is not particularly limited as long as it can remove the non-image portion (non-exposed portion) of the negative photosensitive resin layer. For example, a known developer such as the developer described in Japanese Patent Laid-Open No. 5-72724 can be used. developer. As the developing solution, an aqueous alkaline solution containing a compound having pKa=7 to 13 at a concentration of 0.05 mol/L to 5 mol/L (liter) is preferable. The developer may contain a water-soluble organic solvent and/or a surfactant. As the developer, the developer described in the paragraph 0194 of International Publication No. 2015/093271 is also preferable.

It does not specifically limit as a developing method, It can be any of liquid-covered development, shower development, shower and spin development, and dip development. The shower development refers to a development process in which a developing solution is blown to the exposed negative photosensitive resin layer by a shower to remove a non-exposed portion. After the above-mentioned resin pattern forming step, it is preferable to blow a cleaning agent by a shower, and to remove the development residue while wiping with a brush. The liquid temperature of the developer is not particularly limited, but is preferably 20°C to 40°C.

<Metal pattern forming step> The method of forming a metal pattern of the present invention includes a step of forming a metal pattern having a tapered shape corresponding to the shape of the resin pattern described above (also referred to as a "metal pattern forming step"). The thickness of the metal pattern to be formed is not particularly limited and can be appropriately selected according to needs, but from the viewpoint of the strength and durability of the obtained metal pattern, preferably 5 μm or more, more preferably 10 μm or more, and 12 μm or more For further preference, 15 μm or more is particularly preferred. Moreover, the upper limit is preferably 100 μm or less, and more preferably 50 μm or less.

In the present invention, "the tapered shape corresponding to the shape of the resin pattern in the metal pattern refers to the tapered shape of the metal pattern formed corresponding to the shape of the resin pattern having the tapered shape. As described above, the resin pattern As long as the relationship of W1<W2 is satisfied, when the width (W3) of the top (opposite side of the substrate side) of the metal pattern and the width (W4) of the bottom (the substrate side) of the metal pattern are measured, W3>W4 For example, a metal pattern corresponding to a resin pattern formed in a forward tapered shape, which will be described later, has a reverse tapered shape. In addition, the taper angle of the tapered shape of the metal pattern refers to the angle formed by the side surface of the metal pattern and the base material, and can be approximated to the above-mentioned straight line and the base material when the top end of the metal pattern and the bottom end of the metal pattern are connected by a straight line. The angle formed by the surface. The taper angle of the metal pattern can also be appropriately selected, preferably 100° to 170°, more preferably 110° to 160°, and particularly preferably 120° to 150°.

From the viewpoint of further exhibiting the effects of the present invention, it is preferable that the metal pattern is a metal pattern having an opening having the tapered shape. From the viewpoint of further exerting the effects of the present invention, it is preferable that the metal pattern includes a resin pattern having an opening having a maximum diameter of 100 μm or less on at least one surface in the surface direction of the metal pattern. More preferably, the resin pattern has an opening having a maximum diameter of 50 μm or less on at least one surface in the surface direction, including a metal pattern with an opening having a maximum diameter of 0.1 μm or more on at least one surface in the surface direction. Furthermore, resin patterns of 20 μm or less are more preferable, and resin patterns including openings having a maximum diameter of 0.2 μm or more and 10 μm ² or less on at least one surface in the surface direction of the metal pattern are particularly preferable. Furthermore, from the viewpoint of further exerting the effects of the present invention, it is preferable that the metal pattern includes a resin pattern having an opening area of 1,200 μm ² or less on at least one surface of the metal pattern in the surface direction. More preferably, the resin pattern including openings on at least one surface in the surface direction of the metal pattern has an opening area of 500 μm ² or less, including openings in at least one surface in the surface direction of the metal pattern. A resin pattern having an area of 0.1 μm ² or more and 250 μm ² or less is more preferable, and a resin pattern having an opening having an opening area of 1 μm ² or more and 100 μm ² or less on at least one surface of the metal pattern in the surface direction is Excellent.

The method for forming the metal pattern in the above-mentioned metal pattern forming step is not particularly limited as long as it can form a metal pattern having an inverted tapered shape corresponding to the shape of the resin pattern. casting method). That is, it is preferable that the above-mentioned metal pattern is formed by the electroplating method. As a method of forming a metal pattern by an electroplating method, the following method is mentioned, for example. The electroplating power source is connected to the conductive part of the base material on which the above-mentioned resin pattern is formed, and it is immersed in the electroplating bath for depositing a desired metal. Electroplating is deposited in the form of a film on the exposed portion of the upper surface of the base material, the plated metal is deposited in a range below the thickness of the resin pattern, and the metal pattern in the shape of an inverted cone is grown. Examples of the electroplating bath include nickel sulfamate, a nickel-cobalt alloy bath to which cobalt was added, and the like. In the plating process, the plating thickness is controlled by the current value and the energization or immersion time. In addition, the composition of the electroplating bath, the electroplating treatment temperature, the current value at the time of the electroplating treatment, the electroplating treatment time, etc. are not particularly limited, and can be appropriately selected according to needs. Furthermore, it is not limited to electroplating, and a metal can be deposited by an electroless plating method. Moreover, the electroplating process can be performed in the range of about room temperature (for example, 5 degreeC - 30 degreeC) to 60 degreeC.

Various metals, such as nickel, a nickel-cobalt alloy, an iron-nickel alloy, and copper, can be used for the metal in the said metal pattern. Among them, an iron-nickel alloy containing 30 mass % or more and 45 mass % or less of nickel is preferable, and an alloy of 36 mass % nickel and 64 mass % iron as a main component metal, that is, indium steel, is more preferable. When the material for forming the metal pattern is indium steel, the thermal expansion coefficient of the metal pattern is, for example, about 1.2×10 ⁻⁶ /°C.

<Removal step of resin pattern> Preferably, the method for forming a metal pattern of the present invention further includes a step of removing the resin pattern (also referred to as a "resin pattern removal step") after the step of forming the metal pattern. The removal of the resin pattern in the resin pattern removal step is not particularly limited as a method, but it is preferably performed with a chemical solution. As a method for removing the resin pattern, preferably at 30°C to 80°C, more preferably 50°C to 80°C, immersion in the chemical solution during stirring for 1 minute to 30 minutes includes the resin pattern and the resin pattern. The method of the above-mentioned metal pattern substrate.

Examples of the chemical solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, and organic alkali components such as first-order amine compounds, second-order amine compounds, third-order amine compounds, and fourth-order ammonium salt compounds. A liquid obtained by dissolving in water, dimethyl sulfoxide, N-methylpyrrolidone or these mixed solutions. Moreover, you may remove by a spray method, a spray method, a liquid coating method, etc. using a chemical|medical solution.

<Substrate removal step> Preferably, the method for forming a metal pattern of the present invention further includes a step of removing the above-mentioned substrate from the above-mentioned metal pattern after the step of forming the above-mentioned metal pattern. The metal pattern from which the above-mentioned base material is removed has an opening pattern with an inverted tapered shape and inclined sidewalls complementary to the photoresist pattern, and can be suitably used as a sheet-like metal mask. It does not specifically limit as a method of removing the said base material in the said base material removal process from the said metal pattern, Preferably, the method of peeling the said base material and the said metal pattern is mentioned. In addition, the above-mentioned metal pattern is preferably a pattern in which all metal parts are connected. The said peeling is not specifically limited, For example, the base material can be peeled by extending|stretching in the state folded at 180°. The peeling speed is not particularly limited, but is preferably 1 mm/s to 50 mm/s.

<Other steps> The method for forming a metal pattern of the present invention may include any steps (other steps) other than those described above. There is no restriction|limiting in particular as another process, A well-known process can be mentioned. In addition, as an example of the resin pattern forming step and other steps in the present invention, the method described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be appropriately used in the present invention. In addition, the method for forming a metal pattern of the present invention may include a step of grinding the obtained metal pattern, a step of cleaning the obtained metal pattern, and the like.

<Application of metal pattern> The application of the metal pattern produced by the method for forming a metal pattern of the present invention is not particularly limited, and the above-mentioned metal pattern can be suitably used as a metal pattern for a metal mask, and can be further suitably used as a metal pattern for a metal mask for vapor deposition. , which can be particularly suitably used as a metal pattern for a metal mask for vapor deposition of an organic light-emitting material. In addition, as the above-mentioned organic light-emitting material, red (R), green (G), or blue (B) organic light-emitting materials (RGB organic light-emitting materials) used in organic EL display devices can be appropriately mentioned, and particularly suitable ones can be mentioned. The RGB organic light-emitting materials used in the organic EL light-emitting diodes are described. Moreover, the metal pattern manufactured by the formation method of the metal pattern of this invention can be used suitably as the metal mask for vapor deposition used for manufacture of an organic EL light emitting diode (OLED). Furthermore, there are no particular limitations on other applications of the metal pattern produced by the method for forming the metal pattern of the present invention, and as the application for solder paste printing, dot matrix printing for touch panels, PDP (Plasma printing) can also be used. Display Panel: Fluorescent printing of plasma display panel), etc.

Hereinafter, the negative photosensitive resin layer and the transfer material having the negative photosensitive resin layer used in the present invention will be described in detail.

＜＜Negative photosensitive resin layer＞ The transfer material used in the present invention has at least a negative photosensitive resin layer. The negative photosensitive resin layer may contain a polymerizable compound, a polymerization initiator, and other components.

-Polymerizable compound- It is preferable that the negative photosensitive resin layer contains a polymerizable compound. A polymerizable compound is a compound having a polymerizable base. Examples of the polymerizable base map include a radical polymerizable group and a cationically polymerizable base map, and a radical polymerizable group is preferable from the viewpoint of better curing sensitivity.

It is preferable that the polymerizable compound contains a polymerizable compound having an ethylenically unsaturated group (hereinafter, also simply referred to as an "ethylenically unsaturated compound"). As the ethylenically unsaturated group, a (meth)acryloyl group is preferable.

It is preferable that the ethylenically unsaturated compound contains a bifunctional or more ethylenically unsaturated compound. Here, the "difunctional or more ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.

As an ethylenically unsaturated compound, a (meth)acrylate compound is preferable. Examples of the ethylenically unsaturated compound include, from the viewpoint of film strength after curing, a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth)acrylate compound) and a trifunctional or higher ethylenic unsaturated compound. An unsaturated compound (preferably a tri- or higher functional (meth)acrylate compound) is preferable.

Examples of the bifunctional ethylenically unsaturated compound include tricyclodecanedimethanol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate. meth)acrylate, 1,10-decanediol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate.

Examples of commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate [product name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.], Tricyclodecane dimethanol dimethacrylate [product name: NK Ester DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.], 1,9-nonanediol diacrylate [product name: NK Ester A-NOD -N, manufactured by Shin-Nakamura Chemical Co., Ltd.], 1,10-decanediol diacrylate [product name: NK Ester A-DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.] and 1 , 6-Hexanediol diacrylate [product name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.].

Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipeotaerythritol (tri/tetra/penta/hexa) (meth)acrylate, neotaerythritol (tri/tetra) (methyl) Acrylates, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid(meth)acrylate and glycerol tri(meth)acrylate .

Among them, "(tri/tetra/five/hexa)(meth)acrylate" includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate and hexa(meth)acrylate The concept of acrylic. In addition, "(tri/tetra) (meth)acrylate" is the concept which includes tri (meth)acrylate and tetra (meth)acrylate. The upper limit of the number of functional groups is not particularly limited as the trifunctional or more functional ethylenically unsaturated compound, and for example, it can be set to 20 or less functional groups, and can also be 15 or less functional groups.

As a commercial item of a trifunctional or more than trifunctional ethylenically unsaturated compound, dipivalerythritol hexaacrylate [product name: KAYARAD DPHA, Shin-Nakamura Chemical Co., Ltd.] is mentioned, for example.

Ethylenically unsaturated compounds include 1,9-nonanediol di(meth)acrylate or 1,10-decanediol di(meth)acrylate and dipeotaerythritol (tri/tetra/five/hexa) (Meth)acrylates are more preferred.

Examples of ethylenically unsaturated compounds include caprolactone-modified compounds of (meth)acrylate compounds [KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co. , A-9300-1CL manufactured by Ltd.], alkylene oxide modified compounds of (meth)acrylate compounds [KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Chemical Co., Ltd. ATM-35E, A-9300, DAICEL-ALLNEX LTD.'s EBECRYL (registered trademark) 135, etc.] and ethoxylated glycerol triacrylate [Shin-Nakamura Chemical Co., Ltd. NK Ester A-GLY-9E, etc.].

As an ethylenically unsaturated compound, a urethane (meth)acrylate compound is also mentioned. As the urethane (meth)acrylate compound, a trifunctional or more functional urethane (meth)acrylate compound is preferable. Examples of the trifunctional or higher urethane (meth)acrylate compound include 8UX-015A [manufactured by TAISEI FINE CHEMICAL CO,. LTD.], NK Ester UA-32P [Shin-Nakamura Chemical Co. , manufactured by Ltd.] and NK Ester UA-1100H [manufactured by Shin-Nakamura Chemical Co., Ltd.].

From the viewpoint of improving developability, it is preferable that the ethylenically unsaturated compound contains an ethylenically unsaturated compound having an acid group.

As an acid group, a phosphoric acid group, a sulfonic acid group, and a carboxyl group are mentioned, for example. Among the above, as the acid group, a carboxyl group is preferable.

Examples of the ethylenically unsaturated compound having an acid group include trifunctional to tetrafunctional ethylenically unsaturated compounds having an acid group [derived from a carboxyl group introduced into the neopentaerythritol tri- and tetraacrylate (PETA) skeleton] Compounds (acid value: 80KOH/g to 120mgKOH/g)] and 5- to 6-functional ethylenically unsaturated compounds having acid groups [to dipeutaerythritol pentaacrylate and dipeptaerythritol hexaacrylate (DPHA ) A compound obtained by introducing a carboxyl group into the skeleton (acid value: 25KOH/g to 70mgKOH/g)]. The tri- or more functional ethylenically unsaturated compound which has an acid group can use together the bifunctional ethylenically unsaturated compound which has an acid group as needed.

As the ethylenically unsaturated compound having an acid group, at least one compound selected from the group consisting of an ethylenically unsaturated compound having a carboxyl group having two or more functions and a carboxylic acid anhydride thereof is preferable. When the ethylenically unsaturated compound having an acid group is at least one compound selected from the group consisting of an ethylenically unsaturated compound having a carboxyl group having two or more functions and a carboxylic acid anhydride thereof, developability and film strength are further improved.

Examples of the ethylenically unsaturated compound having a carboxyl group having two or more functions include ARONIX (registered trademark) TO-2349 [manufactured by TOAGOSEI CO., LTD.], ARONIX (registered trademark) M-520 [TOAGOSEI CO., LTD. Manufacturing] and ARONIX (registered trademark) M-510 [manufactured by TOAGOSEI CO., LTD.].

As the ethylenically unsaturated compound having an acid group, a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 can be preferably used, and the contents described in this publication can be referred to by referring to incorporated into this manual.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, further preferably 280 to 2,200, and particularly preferably 300 to 2,200.

Among the ethylenically unsaturated compounds, the content of the ethylenically unsaturated compounds having a molecular weight of 300 or less is preferably 30% by mass or less relative to the content of all ethylenically unsaturated compounds contained in the negative photosensitive resin layer, and 25% by mass % or less is more preferable, and 20 mass % or less is further preferable.

The negative photosensitive resin layer may contain one type of ethylenically unsaturated compound alone, or may contain two or more types of ethylenically unsaturated compounds.

The content of the ethylenically unsaturated compound is preferably 1% by mass to 70% by mass, more preferably 10% by mass to 70% by mass, and more preferably 20% by mass to 60% by mass relative to the total mass of the negative photosensitive resin layer. Preferably, 20% by mass to 50% by mass is particularly preferred. When the negative photosensitive resin layer contains a bifunctional or more ethylenically unsaturated compound, it may further contain a monofunctional ethylenically unsaturated compound.

When the negative photosensitive resin layer contains a bifunctional or more ethylenically unsaturated compound, among the ethylenically unsaturated compounds contained in the negative photosensitive resin layer, the bifunctional or more functional ethylenically unsaturated compound is the main component is better. When the negative photosensitive resin layer contains a bifunctional or more ethylenically unsaturated compound, the content of the bifunctional or more ethylenically unsaturated compound relative to the The content is preferably 60% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.

In the case where the negative photosensitive resin layer contains an ethylenically unsaturated compound having an acid group (preferably an ethylenically unsaturated compound having a carboxyl group having two or more functions or its carboxylic acid anhydride), the ethylenically unsaturated compound having an acid group The content is preferably 1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, and even more preferably 1% by mass to 10% by mass relative to the total mass of the negative photosensitive resin layer.

-Polymerization initiator- It is preferable that the negative photosensitive resin layer contains a polymerization initiator. As a polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator are mentioned, and a photopolymerization initiator is preferable. As the photopolymerization initiator, for example, a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as an "oxime-based photopolymerization initiator".), a photopolymerization initiator having an α-aminoalkylphenone structure, and Photopolymerization initiator (hereinafter, also referred to as "α-aminoalkylphenone-based photopolymerization initiator".), photopolymerization initiator with α-hydroxyalkylphenone structure (hereinafter, also referred to as "α-hydroxyalkylphenone") Referred to as "α-hydroxyalkylphenone-based polymerization initiator"), a photopolymerization initiator having an acylphosphine oxide structure (hereinafter, also referred to as "acylphosphine oxide-based photopolymerization initiator". ) and a photopolymerization initiator having an N-phenylglycine structure (hereinafter, also referred to as "N-phenylglycine-based photopolymerization initiator").

The photopolymerization initiator is selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, α-hydroxyalkylbenzophenone-based polymerization initiators, and N-phenylene At least one of the group of glycine-based photopolymerization initiators is preferably selected from the group consisting of oxime-based photopolymerization initiators, α-aminoalkylphenone-based photopolymerization initiators, and N-benzene At least one of the group of glycine-based photopolymerization initiators is more preferable. Further, as the photopolymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP 2011-095716 A and paragraphs 0064 to 0081 of JP 2015-014783 A can be used.

As a commercial item of a photopolymerization initiator, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(o-benzoyl oxime) [product Name: IRGACURE (registered trademark) OXE-01, manufactured by BASF Corporation], 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone-1 -(o-acetoxime) [Product name: IRGACURE (registered trademark) OXE-02, manufactured by BASF Corporation], [8-[5-(2,4,6-trimethylphenyl)-11-(2- Ethylhexyl)-11H-benzo[a]carbazolyl][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methanone-(o-acetoxime) [Product Name: IRGACURE (registered trademark) OXE-03, manufactured by BASF Corporation], 1-[4-[4-(2-benzofuranylcarbonyl)phenyl]thio]phenyl]-4-methyl-1-pentanone- 1-(o-acetoxime) [Product name: IRGACURE (registered trademark) OXE-04, manufactured by BASF Corporation], 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1-[4-(4-Morolinyl)phenyl]-1-butanone [Product name: IRGACURE (registered trademark) 379EG, manufactured by BASF Corporation], 2-methyl-1-(4-methylthio) Phenyl)-2-endorolinopropan-1-one [Product name: IRGACURE (registered trademark) 907, manufactured by BASF Corporation], 2-hydroxy-1-{4-[4-(2-hydroxy-2 -Methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one [Product name: IRGACURE (registered trademark) 127, manufactured by BASF Corporation], 2-benzyl-2-dimethylamino -1-(4-Merolinophenyl)-butanone-1 [Product name: IRGACURE (registered trademark) 369, manufactured by BASF Corporation], 2-hydroxy-2-methyl-1-phenyl-propane- 1-ketone [Product name: IRGACURE (registered trademark) 1173, manufactured by BASF Corporation], 1-hydroxycyclohexyl phenyl ketone [Product name: IRGACURE (registered trademark) 184, manufactured by BASF Corporation], 2,2-dimethoxy Alkyl-1,2-diphenylethane 1-one [product name: IRGACURE 651, manufactured by BASF Corporation] and oxime ester compound [product name: Lunar (registered trademark) 6, manufactured by DKSH JAPAN K.K.], 1-(linked Benzene-4-yl)-2-methyl-2-endorolinopropan-1-one [product name APi-307 (registered trademark), manufactured by Shenzhen UV-ChemTech LTD], 1-[4-(phenylsulfide) base)phenyl]-3-cyclopentylpropane-1,2-dione-2-(o-benzoyl oxime) [Product name: TR-PBG-305, Changzhou Trolly New Electro nic Materials CO., LTD.], 3-cyclohexyl-1-[9-ethyl-6-(2-furylcarbonyl)-9H-carbazol-3-yl]-1,2-propanedione -2-(o-acetoxime) [Product name: TR-PBG-326, manufactured by Changzhou Trolly New Electronic Materials CO., LTD.], 3-cyclohexyl-1-(6-(2-(benzyloxy) (imino)hexyl)-9-ethyl-9H-carbazol-3-yl)propane-1,2-dione-2-(o-benzoyl oxime) [Product name: TR-PBG -391, manufactured by Changzhou Trolly New Electronic Materials CO., LTD.].

The negative photosensitive resin layer may contain one type of polymerization initiator alone, or may contain two or more types of polymerization initiators. It is preferable that content of a polymerization initiator is 0.1 mass % or more with respect to the total mass of a negative photosensitive resin layer, and it is more preferable that it is 0.5 mass % or more. Moreover, it is preferable that the upper limit of content of a polymerization initiator is 10 mass % or less with respect to the total mass of a negative photosensitive resin layer, and it is more preferable that it is 5 mass % or less.

-Alkali-soluble acrylic resin- The negative photosensitive resin layer may contain an alkali-soluble acrylic resin. By containing an alkali-soluble acrylic resin, the negative photosensitive resin layer improves the solubility of the negative photosensitive resin layer (non-exposed part) to a developing solution.

In this invention, "alkali solubility" means that the dissolution rate calculated|required by the following method is 0.01 micrometer/sec or more. A propylene glycol monomethyl ether acetate solution with a concentration of 25% by mass of the target compound (for example, resin) was applied on a glass substrate, and then heated in an oven at 100° C. for 3 minutes to form a coating film (thickness of the compound) of the above-mentioned compound. 2.0 μm). The dissolution rate (μm/sec) of the coating film was determined by immersing the coating film in a 1 mass % aqueous solution of sodium carbonate (a solution temperature of 30° C.). In addition, when the target compound is not dissolved in propylene glycol monomethyl ether acetate, the target compound is dissolved in an organic solvent (for example, tetrahydrofuran, toluene, or ethanol) having a boiling point of less than 200° C. other than propylene glycol monomethyl ether acetate. .

The alkali-soluble acrylic resin is not limited as long as it has the alkali-soluble acrylic resin described above. Here, "acrylic resin" means a resin containing at least one of a structural unit derived from (meth)acrylic acid and a structural unit derived from (meth)acrylate.

The total ratio of the structural unit derived from (meth)acrylic acid and the structural unit derived from (meth)acrylate in the alkali-soluble acrylic resin is preferably 30 mol % or more, more preferably 50 mol % or more.

In the present invention, when the content of the "structural unit" is specified by the molar fraction (molar ratio), unless otherwise specified, the above-mentioned "structural unit" has the same meaning as the "monomer unit". Moreover, in the present invention, when the resin or polymer has two or more kinds of specific structural units, unless otherwise specified, the content of the above-mentioned specific structural units shall be set to represent the above-mentioned two or more kinds of specific structural units. total content.

From the viewpoint of developability, it is preferable that the alkali-soluble acrylic resin has a carboxyl group. As a method of introducing a carboxyl group into the alkali-soluble acrylic resin, for example, a method of synthesizing the alkali-soluble acrylic resin using a monomer having a carboxyl group can be mentioned. By the above method, the monomer having a carboxyl group is introduced into the alkali-soluble acrylic resin as a structural unit having a carboxyl group. As a monomer which has a carboxyl group, acrylic acid and methacrylic acid are mentioned, for example.

The alkali-soluble acrylic resin may have one carboxyl group, or may have two or more carboxyl groups. Moreover, the structural unit which has a carboxyl group in an alkali-soluble acrylic resin may be single 1 type, and may be 2 or more types.

The content of the structural unit with a carboxyl group is preferably 5 mol % to 50 mol % relative to the total amount of the alkali-soluble acrylic resin, preferably 5 mol % to 40 mol %, and 10 mol % to 30 mol %. Ear% is further preferred.

From the viewpoints of moisture permeability and strength after curing, it is preferable that the alkali-soluble acrylic resin has a structural unit having an aromatic ring. As a structural unit which has an aromatic ring, the structural unit derived from a styrene compound is preferable. As a monomer which forms the structural unit which has an aromatic ring, the monomer which forms the structural unit derived from a styrene compound, and benzyl (meth)acrylate are mentioned, for example.

Examples of monomers that form structural units derived from the above-mentioned styrene compounds include styrene, p-methylstyrene, α-methylstyrene, α,p-dimethylstyrene, and p-ethylstyrene. , p-tertiary butyl styrene, tertiary butoxystyrene and 1,1-diphenylethylene, styrene or α-methyl styrene is preferred, styrene is more preferred.

The constituent unit having an aromatic ring in the alkali-soluble acrylic resin may be one type alone, or two or more types may be used.

When the alkali-soluble acrylic resin has a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5 mol % to 90 mol % relative to the total amount of the alkali-soluble acrylic resin, preferably 10 mol % -90 mol % is more preferred, and 15 mol % - 90 mol % is further preferred.

From the viewpoint of viscosity and strength after curing, it is preferable that the alkali-soluble acrylic resin contains a structural unit having an alicyclic skeleton.

Examples of the aliphatic ring in the alicyclic skeleton include a dicyclopentane ring, a cyclohexane ring, an isoborane ring, and a tricyclodecane ring. Among the above, as the aliphatic ring in the aliphatic cyclic skeleton, a tricyclodecane ring is preferable.

As a monomer which forms the structural unit which has an aliphatic cyclic skeleton, dicyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isocamphenate (meth)acrylate are mentioned, for example.

The structural unit which has an alicyclic skeleton in an alkali-soluble acrylic resin may be single 1 type, or 2 or more types may be sufficient as it.

When the alkali-soluble acrylic resin has a structural unit having an alicyclic skeleton, the content of the structural unit having an aliphatic cyclic skeleton is 5 to 90 mol% relative to the total amount of the alkali-soluble acrylic resin. Preferably, 10 mol% to 80 mol% is more preferred, and 10 mol% to 70 mol% is further preferred.

From the viewpoint of viscosity and strength after curing, it is preferable that the alkali-soluble acrylic resin has a reactive group.

As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. Moreover, when the alkali-soluble acrylic resin has an ethylenically unsaturated group, it is preferable that the alkali-soluble acrylic resin has a structural unit which has an ethylenically unsaturated group in a side chain.

In the present invention, "main chain" represents the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and "side chain" represents an atomic group branched from the main chain.

As the ethylenically unsaturated group, a (meth)acrylic group or a (meth)acryloyloxy group is preferable, and a (meth)acryloyloxy group is more preferable.

The constituent unit having an ethylenically unsaturated group in the alkali-soluble acrylic resin may be one type alone, or two or more types may be used.

When the alkali-soluble acrylic resin has a structural unit having an ethylenically unsaturated group, the content of the structural unit having an ethylenically unsaturated group is 5 to 70 mol% relative to the total amount of the alkali-soluble acrylic resin. Preferably, 10 mol% to 50 mol% is more preferred, and 15 mol% to 40 mol% is further preferred.

As a mechanism for introducing reactive groups into the alkali-soluble acrylic resin, a hydroxyl group, a carboxyl group, a first-order amino group, a second-order amino group, an acetylacetate group, a sulfonic acid group, and the like can be combined with epoxy compounds, intercalation groups, and the like. A method of reacting a segmented isocyanate compound, an isocyanate compound, a vinyl compound, an aldehyde compound, a methylol compound, and a carboxylic acid anhydride.

As a preferable example of the mechanism for introducing the reactive group into the alkali-soluble acrylic resin, after synthesizing an alkali-soluble acrylic resin having a carboxyl group by a polymerization reaction, the carboxyl group of the alkali-soluble acrylic resin is synthesized by a polymer reaction. A part of it reacts with glycidyl (meth)acrylate to introduce the (meth)acryloyloxy group into the mechanism of the alkali-soluble acrylic resin. By the above-mentioned mechanism, the alkali-soluble acrylic resin which has a (meth)acryloyloxy group in a side chain can be obtained.

The above-mentioned polymerization reaction is preferably carried out under a temperature condition of 70°C to 100°C, and more preferably carried out under a temperature condition of 80°C to 90°C. As the polymerization initiator used in the above-mentioned polymerization reaction, an azo-based initiator is preferable, for example, V-601 (product name) or V-65 (product name) manufactured by FUJIFILM Wako Pure Chemical Corporation is more preferable. Moreover, it is preferable to carry out the said polymer reaction under the temperature condition of 80 degreeC - 110 degreeC. In the above-mentioned polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

The weight average molecular weight (Mw) of the alkali-soluble acrylic resin is preferably 10,000 or more, more preferably 10,000 to 100,000, and even more preferably 15,000 to 50,000.

From the viewpoint of developability, the acid value of the alkali-soluble acrylic resin is preferably 50 mgKOH/g or more, more preferably 60 mgKOH/g or more, further more preferably 70 mgKOH/g or more, and particularly preferably 80 mgKOH/g or more. In the present invention, the acid value of the alkali-soluble acrylic resin is a value measured according to the method described in JIS K0070:1992. The upper limit of the acid value of the alkali-soluble acrylic resin is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, from the viewpoint of suppressing dissolution of the exposed negative photosensitive resin layer (exposed portion) in the developing solution.

Hereinafter, specific examples of the alkali-soluble acrylic resin are shown. Moreover, the content ratio (molar ratio) of each structural unit in the following alkali-soluble acrylic resin can be suitably set within the range of the said preferable Mw according to the objective.

[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

The negative photosensitive resin layer may contain a single type of alkali-soluble acrylic resin, or may contain two or more types of alkali-soluble acrylic resins.

From the viewpoint of developability, the content of the alkali-soluble acrylic resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and 25% by mass relative to the total mass of the negative photosensitive resin layer. -70 mass % is more preferable.

-Polymers Containing Constituent Units Having a Carboxylic Anhydride Structure- The negative photosensitive resin layer may further contain a polymer (hereinafter, also referred to as "polymer B") containing a structural unit having a carboxylic acid anhydride structure as a binder. When the negative photosensitive resin layer contains the polymer B, the developability and the strength after curing can be improved.

The carboxylic acid anhydride structure may be any of a chain carboxylic acid anhydride structure and a cyclic carboxylic acid anhydride structure, and a cyclic carboxylic acid anhydride structure is preferred.

As the ring of the cyclic carboxylic acid anhydride structure, a 5-membered ring to a 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.

The structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group obtained by removing two hydrogen atoms from a compound represented by the following formula P-1 in the main chain, or a structural unit derived from the following formula P-1. The monovalent group obtained by removing one hydrogen atom in the represented compound is preferably a structural unit bonded to the main chain directly or via a divalent linking group.

[Chemical formula 4]

In formula P-1, R ^A1a represents a substituent, n ^1a R ^A1a may be the same or different, and Z ^1a represents a divalent group forming a ring containing -C(=O)-OC(=O)- , and n ^1a represents an integer greater than or equal to 0.

As a substituent represented by R ^A1a , an alkyl group is mentioned, for example.

As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is further preferable.

n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.

When n ^1a represents an integer of 2 or more, plural R ^A1a may be the same or different. In addition, the R ^A1a present in plural may be bonded to each other to form a ring, but it is preferable that they be bonded to each other and not to form a ring.

As the constitutional unit having a carboxylic acid anhydride structure, a constitutional unit derived from an unsaturated carboxylic acid anhydride is preferable, a constitutional unit derived from an unsaturated cyclic carboxylic acid anhydride is more preferable, and a constitutional unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is more preferable. For further preference, the structural unit derived from maleic anhydride or itaconic anhydride is particularly preferred, and the structural unit derived from maleic anhydride is most preferred.

The constituent unit having a carboxylic acid anhydride structure in the polymer B may be one type alone, or two or more types may be used.

The content of the constituent unit having a carboxylic acid anhydride structure is preferably 0 mol% to 60 mol% relative to the total amount of the polymer B, preferably 5 mol% to 40 mol%, and 10 mol% to 35 mol%. Molar % is further preferred.

The negative photosensitive resin layer may contain one type of polymer B alone, or may contain two or more types of polymer B.

When the negative photosensitive resin layer contains the polymer B, the content of the polymer B is 0.1% by mass to 30% by mass relative to the total mass of the negative photosensitive resin layer from the viewpoints of developability and strength after curing. More preferably, 0.2 to 20 mass % is more preferable, 0.5 to 20 mass % is further preferable, and 1 to 20 mass % is particularly preferable.

-Surfactant- The negative photosensitive resin layer can contain a surfactant. As the surfactant, for example, the surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of Japanese Patent Laid-Open No. 2009-237362 can be mentioned.

Examples of the surfactant include fluorine-based surfactants, silicon-based surfactants (also referred to as silicone-based surfactants), nonionic surfactants, and the like, fluorine-based surfactants or silicone-based surfactants. agent is better. Examples of commercially available fluorine-based surfactants include Megaface (registered trademark) F-171, F-172, F-173, F-176, F-177, F-141, F-142, F -143, F-144, F-437, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F-556 , F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-41 , R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (the above are DIC Corporation), Fluorad (registered trademark) FC430, FC431, FC171 (the above are manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-382, SC-101, SC-103, SC-104, SC-105, SC- 1068, SC-381, SC-383, S-393, KH-40 (the above are manufactured by AGC Inc.), PolyFox (registered trademark) PF636, PF656, PF6320, PF6520, PF7002 (the above are manufactured by OMNOVA Solutions Inc.), FTERGENT (registered trademark) 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F (the above are manufactured by NEOS Corporation) and the like.

As the fluorine-based surfactant, an acrylic-based compound can also be preferably used. The acrylic-based compound has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cleaved and the fluorine atom is removed. Atomic volatilization. Examples of such fluorine-based surfactants include Megaface (registered trademark) DS series manufactured by DIC CORPORATION (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), For example, Megaface (registered trademark) DS-21 can be mentioned. As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. A block polymer can also be used as a fluorine-type surfactant. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, and the fluorine-containing polymer compound includes: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; The repeating unit of the (meth)acrylate compound of preferably 5 or more) alkeneoxy group (preferably etheneoxy group and propoxy group).

As the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated bond-containing group in a side chain can also be used. Megaface (registered trademark) RS-101, RS-102, RS-718K, RS-72-K (the above are manufactured by DIC Corporation), etc. are mentioned.

Examples of the silicone-based surfactant include linear polymers composed of siloxane bonds, and modified siloxane polymers obtained by introducing organic groups to side chains or terminals. Specific examples of commercially available silicone-based surfactants include DOWSIL (registered trademark) 8032 ADDITIVE, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are manufactured by Dow Corning Toray Co., Ltd.) and X-22-4952, X-22-4272, X-22-6266, KF-351A, K354L, KF- 355A, KF-945, KF-640, KF-642, KF-643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001, KF-6002 (Shin- Etsu Chemical Co., Ltd.), F-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), BYK307, BYK323, BYK330 (the above are BYK Chemie GmbH), etc.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) base, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diethyl ether Laurate, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (the above are manufactured by BASF), TETRONIC ( Registered trademarks) 304, 701, 704, 901, 904, 150R1 (the above are manufactured by BASF Corporation), SOLSPERSE (registered trademark) 20000 (the above are manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (the above are manufactured by FUJIFILM Wako Pure Chemical Corporation), Pionin (registered trademark) D-6112, D-6112-W, D-6315 (the above are manufactured by TAKEMOTO OIL & FAT Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (the above are manufactured by Nissin Chemical Industry Co., Ltd.), etc.

The negative photosensitive resin layer may contain one type of surfactant alone, or may contain two or more types of surfactants.

When the negative photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3% by mass, and preferably 0.05% by mass to 1% by mass relative to the total mass of the negative photosensitive resin layer. More preferably, 0.1 mass % - 0.8 mass % are more preferable.

-Other ingredients- The negative photosensitive resin layer may contain components other than the components described above (hereinafter, also referred to as "other components"). As other components, for example, heterocyclic compounds, aliphatic thiol compounds, blocked isocyanate compounds, hydrogen donating compounds, particles (for example, metal oxide particles), and coloring agents can be mentioned. Further, as other components, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 and the other additives described in paragraphs 0058 to 0071 of Japanese Patent Laid-Open No. 2000-310706 can also be mentioned.

The negative photosensitive resin layer can be formed by drying the coating layer composed of the above-mentioned coating liquid for forming a negative photosensitive resin layer. The formation of the negative photosensitive resin layer will be described in detail in the section of the transfer material.

-Impurities in the negative photosensitive resin layer- From the viewpoint of improving reliability and patternability, it is preferable that the content of impurities in the negative photosensitive resin layer is small. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, and ions of these and halide ions (chloride ions, bromide ions, etc.) ions, iodide ions, etc.), etc. Among them, since sodium ions, potassium ions, and chloride ions are easily mixed as impurities, the following contents are particularly preferable. In terms of mass, the content of impurities in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less. The lower limit can be made 0.01 ppm or more, and can be made 0.1 ppm or more on a mass basis. As a method of reducing the impurities to the above-mentioned range, selection of materials that do not contain impurities in the raw materials of each layer, prevention of contamination of impurities when the layers are formed, and removal by cleaning, etc. are mentioned. By this method, the amount of impurities can be set within the above-mentioned range. For example, impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectrometry, atomic absorption spectrometry, and ion chromatography.

Moreover, benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylformamide in the negative photosensitive resin layer It is preferable that the content of compounds such as ethylacetamide and hexane is small. The content of these compounds in each layer is preferably 1,000 ppm or less, more preferably 200 ppm or less, and particularly preferably 40 ppm or less on a mass basis. The lower limit is not particularly limited, but from the viewpoint of a realistically lowerable limit and a measurement limit, it can be set to 10 ppb or more, and can be set to 100 ppb or more on a mass basis. The impurity of the compound can be suppressed in content in the same manner as the impurity of the metal described above. Moreover, it can quantify by a well-known measurement method.

Although the negative photosensitive resin layer was described above, it is preferable to set the same impurity amount for the resin pattern formed from the negative photosensitive resin layer.

-Thickness of negative photosensitive resin layer Although it can select suitably as thickness of a negative photosensitive resin layer, 10 micrometers or more are preferable, 15 micrometers or more are more preferable, 20 micrometers or more are still more preferable, and 30 micrometers or more are especially preferable. In addition, the upper limit is preferably 100 μm or less.

-Method for forming a negative photosensitive resin layer- The negative-type photosensitive resin layer can be formed by preparing a negative-type photosensitive resin composition containing the components and solvent used in the formation of the negative-type photosensitive resin layer, and by coating and drying. It is also possible to prepare a composition by dissolving each component in a solvent in advance as a solution, and then mixing the obtained solutions at a predetermined ratio. The composition prepared as described above can be filtered using, for example, a filter having a pore diameter of 0.2 μm to 30 μm. The negative photosensitive resin layer can be formed by coating the negative photosensitive resin composition on the dummy support or the coverlay and drying it. The coating method is not particularly limited, and the coating can be performed by known methods such as slit coating, spin coating, curtain coating, die coating, and inkjet coating. Moreover, it is also possible to form a negative photosensitive resin layer on a dummy support or a coverlay film after forming an intermediate layer or other layers to be described later.

-Negative photosensitive resin composition- It is preferable that the negative photosensitive resin composition contains the component and solvent used for formation of a negative photosensitive resin layer. The negative photosensitive resin layer can be appropriately formed by adding a solvent to each component to adjust the viscosity, and performing coating and drying.

It is preferable that the negative photosensitive resin composition contains a solvent. As a solvent, an organic solvent is preferable. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (alias: 1-methoxy-2-propyl acetate), and diethylene glycol ethyl methyl ether. ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam, n-propanol and 2-propanol. As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.

As the solvent, the solvents described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073 can also be used, the contents of which are incorporated herein by reference. Moreover, as a solvent, the organic solvent (high boiling point solvent) whose boiling point is 180 degreeC - 250 degreeC can also be used as needed. The negative photosensitive resin composition may contain one type of solvent alone, or may contain two or more types of solvents. When the negative-type photosensitive resin composition contains a solvent, the total solid content of the negative-type photosensitive resin composition is preferably 5% by mass to 80% by mass relative to the total mass of the negative-type photosensitive resin composition. It is more preferable that it is mass % - 40 mass %, and 5 mass % - 30 mass % is still more preferable.

When the negative-type photosensitive resin composition contains a solvent, the viscosity of the negative-type photosensitive resin composition at 25°C is, for example, preferably 1 mPa·s to 50 mPa·s, preferably 2 mPa·s, from the viewpoint of coatability. ∼40mPa·s is more preferable, and 3mPa·s∼30mPa·s is further preferable. Viscosity is measured using a viscometer. As the viscometer, for example, a viscometer manufactured by TOKI SANGYO CO., LTD. (product name: VISCOMETER TV-22) can be preferably used. However, the viscometer is not limited to the above-mentioned viscometer.

When the negative-type photosensitive resin composition contains a solvent, for example, from the viewpoint of coatability, the surface tension of the negative-type photosensitive resin composition at 25°C is preferably 5mN/m to 100mN/m, preferably 10mN /m～80mN/m is more preferable, and 15mN/m～40mN/m is more preferable. Surface tension is measured using a surface tensiometer. As the surface tensiometer, for example, a surface tensiometer (product name: Automatic Surface Tensiometer CBVP-Z) manufactured by Kyowa Interface Science Co., Ltd. can be preferably used. However, the surface tensiometer is not limited to the above-mentioned surface tensiometer.

＜＜Transfer material＞＞ The transfer material used in the present invention preferably has at least a negative-type photosensitive resin layer, and preferably has at least a dummy support and a negative-type photosensitive resin layer.

-pseudo-support- The transfer material used in the present invention preferably has a dummy support. The pseudo-support system supports the negative photosensitive resin layer and can be peeled off. When exposing the negative photosensitive resin layer to the dummy support used in the present invention, it is preferable to have light transmittance from the viewpoint of being able to expose the negative photosensitive resin layer through the dummy support. Having light transmittance means that the transmittance of the dominant wavelength of light used in pattern exposure is 50% or more, and from the viewpoint of improving exposure sensitivity, the transmittance of the dominant wavelength of light used in pattern exposure is 60% or more. Good, more than 70% is better. As a measurement method of transmittance, the method of measurement using the MCPD Series by Otsuka Electronics Co., Ltd. is mentioned. As a dummy support, a glass substrate, a resin film, paper, etc. are mentioned, From a viewpoint of intensity|strength, flexibility, etc., a resin film is especially preferable. As a resin film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. are mentioned. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferred.

The thickness of the dummy support is not particularly limited, but the range of 5 μm to 200 μm is preferable, and the range of 10 μm to 150 μm is more preferable from the viewpoints of ease of handling and versatility. The thickness of the dummy support may be selected according to the material from the viewpoints of strength as a support, flexibility required for bonding to a base material, and light transmittance required for exposure.

A preferable aspect of the dummy support is described in, for example, paragraphs 0017 to 0018 of Japanese Patent Laid-Open No. 2014-85643, and the contents of this publication are incorporated into the present invention.

-cover film- The transfer material used in the present invention preferably has a cover film on the surface opposite to the surface on which the dummy support is provided in the transfer material. As a coverlay film, a resin film, paper, etc. are mentioned, From a viewpoint of strength, flexibility, etc., a resin film is particularly preferable. As a resin film, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. are mentioned. Among them, polyethylene film, polypropylene film and polyethylene terephthalate film are preferred.

The average thickness of the coverlay film is not particularly limited, and, for example, a thickness of 1 μm to 2 mm can be preferably used.

-middle layer- The transfer material or the above-mentioned laminate used in the present invention may have an intermediate layer (for example, a water-soluble resin layer). It is preferable that the intermediate layer contains a polymer described later.

〔polymer〕 The intermediate layer can contain a polymer. As the polymer used in the intermediate layer, a water-soluble resin or an alkali-soluble resin is preferable. In the present invention, "water solubility" means that the solubility in 100 g of pH 7.0 water at 22°C is 0.1 g or more, and "alkali solubility" means the solubility in 100 g of a 1 mass % aqueous solution of sodium carbonate at 22°C 0.1 g or more. In addition, the above-mentioned "water-solubility and alkali-solubility" may be either water-soluble or alkali-soluble, or may be water-soluble and alkali-soluble. In addition, the solubility of the polymer in 100 g of water at pH 7.0 at 22° C. is preferably 1 g or more, and more preferably 5 g or more. Examples of water-soluble resins include cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, and vinyl ether resins. , polyamide resins and these copolymers and other resins. Among them, cellulose resin is preferred, and at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropyl methyl cellulose is more preferred. As the alkali-soluble resin, an alkali-soluble acrylic resin is preferable, and an acrylic resin having an acid group capable of forming a salt is more preferable.

The intermediate layer may contain one type of polymer alone, or may contain two or more types. From the viewpoint of adhesiveness, the content of the polymer is preferably 20% by mass to 100% by mass, and more preferably 50% by mass to 100% by mass relative to the total mass of the intermediate layer.

[Ultraviolet absorber] The intermediate layer may have a UV absorber in order to control absorption. The ultraviolet absorber is not particularly limited as long as it is a compound that absorbs ultraviolet rays having a wavelength of 400 nm or less. Examples of the ultraviolet absorber include ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds, benzoate compounds, salicylate compounds, trisulfuric acid compounds, and cyanoacrylate compounds. Specifically, for example, 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)- 4-6-bis(1-methyl-1-phenylethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(third Butyl)phenol, 2-(2H-benzotriazol-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1, 1,3,3-Tetramethylbutyl)phenol, etc. or mixtures thereof, modifications, polymers, derivatives, etc. Moreover, for example, 2-(4,6-diphenyl-1,3,5-tris-2-yl)-5-[(hexyl)oxy]phenol, 2- [4-[(2-Hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5 -Tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylbenzene base)-1,3,5-tris𠯤, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-mesostris, etc. or such mixtures, modifications, polymers, derivatives, etc. These may be used alone, or a plurality of them may be mixed and used. The content of the ultraviolet absorbing material is not particularly limited, and may be appropriately set as an amount to set the optical density of the photosensitive resin layer to a desired value.

[Surfactant] From the viewpoint of thickness uniformity, it is preferable to contain a surfactant in the intermediate layer. As the surfactant, any one of a surfactant having a fluorine atom, a surfactant having a silicon atom, and a surfactant not having a fluorine atom and a silicon atom can be used. Among them, as the surfactant, from the viewpoint of suppressing the occurrence of streaks in the negative photosensitive resin layer and the intermediate layer and the adhesiveness, those having a fluorine atom are preferred, and those having a perfluoroalkyl group and a polyalkylene are preferred. Oxygen-based surfactants are more preferred. Moreover, as a surfactant, any of anionic, cationic, nonionic (nonionic) or amphoteric can be used, and a preferable surfactant is a nonionic surfactant. From the viewpoint of suppressing precipitation of the surfactant, the solubility of the surfactant in 100 g of water at 25° C. is preferably 1 g or more.

The intermediate layer may contain one type of surfactant alone, or may contain two or more types. From the viewpoint of suppressing the occurrence of streaks and adhesiveness in the negative photosensitive resin layer and the intermediate layer, the content of the surfactant in the intermediate layer is preferably 0.05% by mass to 2.0% by mass relative to the total mass of the intermediate layer. It is preferable, 0.1 mass % - 1.0 mass % are more preferable, and 0.2 mass % - 0.5 mass % are especially preferable.

[Inorganic filler] The intermediate layer can contain an inorganic filler. The inorganic filler in the present invention is not particularly limited. Silica particles, alumina particles, zirconia particles, etc. are mentioned, and silica particles are more preferred. From the viewpoint of transparency, particles having a small particle diameter are preferred, and those having an average particle diameter of 100 nm or less are more preferred. For example, if it is a commercial item, NOWTEX (registered trademark) can be used suitably.

From the viewpoint of the adhesiveness between the intermediate layer and the negative photosensitive resin layer, the volume fraction of the particles in the intermediate layer (the volume ratio of the particles in the intermediate layer) is 5% with respect to the total volume of the intermediate layer. -90% is more preferable, 10-80% is more preferable, and 20-60% is further preferable.

[pH adjuster] A pH adjuster can be included in the intermediate layer. By including pH adjustment, the agent can further stably maintain the color development state or decolorization state of the dye in the intermediate layer, and further improve the adhesiveness between the negative photosensitive resin layer and the intermediate layer. The pH adjuster in the present invention is not particularly limited. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amine, organic ammonium salt, etc. are mentioned. From the viewpoint of water solubility, sodium hydroxide is preferred. From the viewpoint of the adhesiveness between the negative photosensitive resin layer and the intermediate layer, an organic ammonium salt is preferable.

[The thickness of the intermediate layer] The thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 2 μm, from the viewpoint of the adhesiveness and pattern formability between the negative photosensitive resin layer and the intermediate layer. Moreover, it is preferable that the thickness of an intermediate layer is thinner than the thickness of a negative photosensitive resin layer.

The intermediate layer can have two or more layers. When the intermediate layer has two or more layers, the thickness of each layer is not particularly limited as long as it is within the above-mentioned range. Among the two or more layers, the thickness of the layer closest to the negative photosensitive resin layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 2 μm.

[Method of forming the intermediate layer] The intermediate layer in the present invention can be formed by preparing a composition for forming an intermediate layer containing a component for forming the intermediate layer and a water-soluble solvent, and applying and drying. It is also possible to prepare a composition by dissolving each component in a solvent in advance as a solution, and then mixing the obtained solution at a predetermined ratio. The composition prepared in the above manner can be filtered using a filter or the like having a pore size of 3.0 μm. The intermediate layer can be formed on the dummy support by applying the intermediate layer-forming composition to the dummy support and drying it. The coating method is not particularly limited, and it can be applied by known methods such as slit coating, spin coating, curtain coating, and inkjet coating.

It is preferable that the intermediate layer-forming composition contains the components for forming the intermediate layer and a water-soluble solvent. The intermediate layer can be appropriately formed by adding a water-soluble solvent to each component to adjust the viscosity, and performing coating and drying.

As a water-soluble solvent, a well-known water-soluble solvent can be used, for example, water, a C1-C6 alcohol, etc. are mentioned, It is preferable to contain water. Specific examples of the alcohol having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol. Among them, it is preferable to use at least one selected from the group consisting of methanol, ethanol, n-propanol and isopropanol.

-other layers- The transfer material of the present invention may have layers other than the above (hereinafter, also referred to as "other layers"). As another layer, a thermoplastic resin layer etc. are mentioned. Preferred aspects of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP 2014-85643 A, and further preferred aspects of other layers are described in JP 2014-85643 A, paragraphs 0194 to 0196 It is described in each paragraph, and the contents of the gazette are incorporated into this specification.

-Manufacturing method of transfer material- The manufacturing method of the transfer material used by this invention is not specifically limited, A well-known manufacturing method, for example, a well-known formation method of each layer, etc. can be used. Moreover, after forming the negative photosensitive resin layer on the dummy support, it is preferable that the manufacturing method of a transfer material further includes the step of providing a cover film on the negative photosensitive resin layer. In addition, after the transfer material is produced, the transfer material in the form of a roll can be produced and stored by winding the transfer material. The transfer material in the form of a roll can be provided in the form of being bonded to the base material by a roll-to-roll method.

(Manufacturing method of metal mask for vapor deposition) The manufacturing method of the metal mask for vapor deposition of this invention includes the manufacturing method of the metal mask for vapor deposition which forms a metal pattern by the formation method of the metal pattern of this invention. Moreover, the manufacturing method of the metal mask for vapor deposition of the present invention preferably includes the steps of: preparing a laminate having a negative-type photosensitive resin layer on a base material; setting from the negative-type photosensitive resin layer A step of exposing the negative photosensitive resin layer through the exposure mask with light having a component obliquely incident in the thickness direction of the exposure mask on the side opposite to the side with the substrate; A step of developing the exposed negative photosensitive resin layer to form a tapered resin pattern; and a step of forming a tapered metal pattern corresponding to the shape of the resin pattern. In addition, the manufacturing method of the metal mask for vapor deposition of the present invention may include each step in the above-described method of forming the metal pattern of the present invention, and the preferred aspects are also the same. Moreover, the metal mask for vapor deposition manufactured by the manufacturing method of the metal mask for vapor deposition of this invention may have other members besides the said metal pattern. It does not specifically limit as another member, A well-known member used for the metal mask for vapor deposition can be used.

(Method of Manufacturing Organic Light Emitting Diode and Method of Manufacturing Organic EL Display Device) The manufacturing method of the organic light emitting diode of this invention or the manufacturing method of the organic EL display device of this invention uses the metal pattern obtained by the formation method of the metal pattern of this invention. Further, the method for producing an organic light emitting diode of the present invention or the method for producing an organic EL display device of the present invention includes using the metal pattern obtained by the method for forming a metal pattern of the present invention as a metal mask for vapor deposition. The steps are preferably, the metal pattern obtained by the method for forming the metal pattern of the present invention is used as a metal mask for vapor deposition of organic light-emitting material, and the steps of vapor-depositing the organic light-emitting material onto the substrate are more preferable. As said organic light-emitting material, the organic light-emitting material of red (R), green (G), or blue (B) is mentioned. Furthermore, the manufacturing method of the organic light emitting diode of the present invention or the manufacturing method of the organic EL display device of the present invention may include each step in the above-mentioned method of forming the metal pattern of the present invention, and the preferred embodiments are also the same. Moreover, the manufacturing method of the organic light emitting diode of this invention or the manufacturing method of the organic EL display device of this invention may include well-known processes other than the above. [Example]

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are based on mass.

<Measurement of scattering angle of scattering layer> Using Goniometer GP-200 manufactured by MURAKAMI COLOR RESEARCH LABORATORY CO., LTD., light was perpendicularly incident on the scattering layer, and the intensity of the transmitted light was measured in an angular range from plus 90° to minus 90°. With respect to the intensity of 0°, the scattering angle is defined as the full-angle width which is half of the intensity.

<Preparation of negative photosensitive resin compositions 1 and 2> Negative photosensitive resin compositions 1 and 2 were prepared by adding methyl ethyl ketone after mixing to the composition shown in the following Table 1 (in Table 1, described as compositions 1 and 2. Solid content concentration: 25% by mass).

【Table 1】 Ingredient (numerical value of each ingredient: parts by mass) Composition 1 Composition 2 Alkali-soluble acrylic resin Styrene/methacrylic acid/methyl methacrylate=32/28/40 (mass %) copolymer, Mw=40,000 - 55.00 Copolymer of styrene/methacrylic acid/methyl methacrylate=52/29/19 (mass %), Mw=60,000 50.00 - Benzyl methacrylate/methacrylic acid = 81/19 (mass %) copolymer, Mw = 40,000 - - polymeric compound BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) 36.20 20.20 BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.) - 9.80 Dimethacrylate of polyethylene glycol obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A, respectively - - M-270 (manufactured by TOAGOSEI CO., LTD.) 5.00 - A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) - 10.00 SR-454 (manufactured by Arkema SA) - - SR-502 (manufactured by Arkema SA) - - A-9300-CL1 (manufactured by Shin-Nakamura Chemical Co., Ltd.) - - polymerization initiator B-CIM (manufactured by KUROGANE KASEI Co., Ltd.) 7.00 3.00 Sensitizer SB-PI 701 (manufactured by SANYO KASEI CO., LTD.) 0.50 0.50 chain transfer agent Colorless Crystal Violet (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.40 0.90 N-Phenylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.20 - Colorant Malachite Green (manufactured by Tokyo Chemical Industry Co., Ltd.) - 0.05 Rust inhibitor CBT-1 (manufactured by JOHOKU CHEMICAL CO., LTD.) 0.10 - 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6-carboxybenzotriazole mass ratio) mixture - 0.14 polymerization inhibitor TDP-G (manufactured by Kawaguchi Chemical Industry Co., Ltd.) 0.30 0.10 Irganox245 (manufactured by BASF) - - N-nitrosophenylhydroxylamine aluminum salt (manufactured by FUJIFILM Wako Pure Chemical Corporation) - - Antioxidants Phenidone (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.01 0.01 Surfactant F-552 (manufactured by DIC Corporation) 0.29 0.30

In addition, the details of the compounds described in Table 1 are shown below. BPE-500: 2,2-bis(4-(methacryloyloxypentaethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. BPE-200: 2,2-bis(4-(methacryloyloxydiethoxy)phenyl)propane, manufactured by Shin-Nakamura Chemical Co., Ltd. M-270: Polypropylene glycol diacrylate, manufactured by TOAGOSEI CO., LTD. A-TMPT: Trimethylolpropane triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. SR-454: Ethoxylated (3) trimethylolpropane triacrylate, manufactured by SARTOMER SR-502: Ethoxylated (9) trimethylolpropane triacrylate, manufactured by SARTOMER A-9300-CL1: ε-caprolactone-modified tris-(2-propenyloxyethyl)isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd. B-CIM: Photoradical generator (photopolymerization initiator), manufactured by Hampford Corporation, 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer SB-PI 701: Sensitizer, 4,4'-bis(diethylamino)benzophenone, manufactured by Sanyo Trading Co., Ltd. CBT-1: Rust inhibitor, carboxybenzotriazole, manufactured by JOHOKU CHEMICAL CO., LTD. TDP-G: Polymerization inhibitor, phenothia, manufactured by Kawaguchi Chemical Industry Co., Ltd. Irganox245: Hindered phenolic polymerization inhibitor, manufactured by BASF F-552: Fluorine-based surfactant, Megaface F552, manufactured by DIC CORPORATION

<Preparation of transfer material A> On a dummy support of a polyethylene terephthalate film (16KS40: product name, TORAY INDUSTRIES, INC.) having a thickness of 16 μm, using a bar coater, the thickness of the dried negative-type photosensitive resin layer was measured. After adjusting the coating amount of the negative photosensitive resin composition 1 so as to be 10 μm, the negative photosensitive resin composition 1 was applied and then dried in an oven at 80° C. to form a negative photosensitive resin layer. Next, a transfer material A was produced by pressing polyethylene terephthalate (16KS40: product name, TORAY INDUSTRIES, INC.) with a thickness of 16 μm to the surface of the negative photosensitive resin layer as a cover film.

<Preparation of transfer material B> A polyethylene terephthalate film (16KS40: product name, TORAY INDUSTRIES, INC.) with a thickness of 16 μm, that is, a dummy support, was coated with a bar coater so that the thickness after drying would be 1 μm The following water-soluble resin composition was dried in an oven at 90° C. to form a water-soluble resin layer as an intermediate layer. Then, on the water-soluble resin layer, using a bar coater, the coating amount of the negative photosensitive resin composition 2 was adjusted so that the thickness of the negative photosensitive resin layer after drying was 10 μm, and the negative photosensitive resin composition 2 was applied. After the photosensitive resin composition 2, it was dried in an oven at 80°C, and a negative photosensitive resin layer was formed. Next, a transfer material B was produced by press-bonding polyethylene terephthalate (16KS40: product name, TORAY INDUSTRIES, INC.) with a thickness of 16 μm as a cover film on the surface of the negative photosensitive resin layer.

-Composition of water-soluble resin composition- · Ion-exchanged water: 38.12 parts · Methanol (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC.): 57.17 parts ・KURARAY POVALPVA-205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.): 3.22 parts ・Polyvinylpyrrolidone K-30 (manufactured by NIPPON SHOKUBAI CO., LTD.): 1.49 parts Megaface F-444 (fluorine-based nonionic surfactant, manufactured by DIC CORPORATION): 0.0015 parts

<Preparation of transfer material C> A transfer material C was produced in the same manner as the production of the transfer material A, except that the thickness of the dried negative photosensitive resin layer was 8 μm.

<Preparation of transfer material D> A transfer material D was produced in the same manner as the production of the transfer material A, except that the thickness of the dried negative photosensitive resin layer was 20 μm.

(Example 1) <Formation of laminated body> The cover film of the transfer material A prepared above was peeled off, and the surface of the exposed negative-type photosensitive resin layer was subjected to Ni plating (thickness 100nm) on the conductive substrate on the glass. The type photosensitive resin layer and the dummy support were laminated to obtain a laminate (preparation step). -Lamination conditions- Temperature of substrate: 80℃ Temperature of rubber roller: 110℃ Line pressure: 3N/cm Transmission speed: 2m/min

<Formation of Resin Pattern> Next, an exposure mask (line/space=20 μm/20 μm, line length 100 μm) was brought into close contact with the surface of the dummy support of the obtained laminate. Then, on the exposure mask, a lens diffuser (registered trademark) LSD60ACUVT30 (scattering angle: 60°, diffuse transmittance: 95%, material: UV-transmitting acrylic resin) manufactured by OPTICAL SOLUTIONS Corporation was arranged as a scattering layer. The exposure mask and the scattering layer are arranged so as not to be in contact with each other. In Table 2, the scattering layer used in Example 1 is described as "resin layer having irregularities". Using a high pressure mercury lamp exposure machine (MAP-1200L manufactured by Japan Science Engineering Co., Ltd., dominant wavelength: 365 nm), irradiation was performed by transmitting light through the dummy support, and the negative photosensitive resin layer was irradiated at 150 mJ/cm ² . pattern exposure (pattern exposure step). After peeling off the dummy support, spray development was performed for 50 seconds using an aqueous sodium carbonate solution having a liquid temperature of 25° C., thereby forming a resin pattern having a tapered shape (resin pattern forming step).

<Observation of cross-sectional shape of resin pattern (evaluation of tapered shape)> The cross-sectional shape of the obtained resin pattern was observed with an electron microscope (SEM) at any 10 positions on the substrate surface, and as shown in FIG. 5 , the width (W1) of the top of the pattern and the width of half of the layer thickness of the pattern were measured. (W2), the width (W3) of the pattern bottom, and the layer thickness (W4), the value of tan (W4/((W3-W1)/2)) was calculated using the respective average values. Below, evaluation criteria are shown. A: W3>W2>W1 is satisfied, and the above value is less than 5.67. B: W3>W2>W1 is satisfied, and the above-mentioned value is 5.67 or more. C: W3>W2>W1 is not satisfied.

<Formation of metal pattern> Electrolytic plating using the conductive substrate as an electrode was performed as follows, and an electrodeposit (metal pattern) having a thickness of about 7 μm was deposited on a region on the conductive substrate where the resin pattern was not formed. In the electroplating bath heated to 50°C, the electroplating solution was added, the conductive base material prepared as a cathode was placed, and a nickel plate was placed as an anode, respectively, and a power source was connected. Next, the power source was operated, and a current was passed between the conductive substrate and the nickel plate for about 60 minutes, respectively. A nickel plating layer (metal pattern) is formed on the surface of the conductive substrate where the resin pattern is not formed (metal pattern forming step).

<Removal of resin pattern> Next, the resin pattern was removed by immersing for 60 seconds in a 5 mass % triethylamine aqueous solution (boiling point 89° C.) adjusted to 40° C. to form a metal pattern having a tapered shape on the substrate.

<Peeling of base material> A metal mask having a metal pattern was obtained by stretching and peeling the conductive base material on which the metal pattern was formed above at 50 mm/s and 180-degree folded state.

<Observation of cross-sectional shape (evaluation of tapered shape)> The cross-sectional shape of the obtained metal pattern was observed with an electron microscope (SEM) at 10 arbitrary locations within the substrate surface, and as shown in FIG. 6 , the width (W5) of the top of the pattern and the width of half of the layer thickness of the pattern were measured. (W6), the width (W7) of the pattern bottom, and the layer thickness (W8), the value of tan (W8/((W5-W7)/2)) was calculated using the respective average values. Below, evaluation criteria are shown. A: W5>W6>W7 is satisfied, and the above value is less than 5.67. B: W5>W6>W7 is satisfied, and the above-mentioned value is 5.67 or more. C: W5>W6>W7 is not satisfied.

<Exposure level margin> The cross-sectional shape of the resin pattern obtained in the same manner as the above-mentioned formation of the resin pattern was observed in the same manner as above except that the exposure amount was changed by ±5% and the exposure was performed, and as shown in FIG. The width (W1), the width at half the film thickness of the pattern (W2), the width at the bottom of the pattern (W3), and the film thickness (W4) were calculated using the average values of tan (W4/((W3-W1) /2)) value. In the above case, the evaluation was performed in the same manner as the observation of the cross-sectional shape of the resin pattern (taper shape evaluation). A: The resin pattern produced by exposure with an exposure amount varying by ±5% satisfies W3>W2>W1, and the above value is less than 5.67. B: The resin pattern produced by exposing with an exposure amount varying by ±5% satisfies W3>W2>W1, and the above value is 5.67 or more. C: The resin pattern produced by exposure with an exposure amount varying by ±5% does not satisfy W3>W2>W1.

(Examples 2 to 9 and Comparative Examples 1 and 2) As described in Table 2, except that the exposure method and the transfer material were changed, the resin pattern and the metal pattern were formed in the same manner as in Example 1, and the evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 2. More specifically, it is as follows.

In Example 2, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that the scattering layer used in Example 1 was changed to another scattering layer containing a layer of a specific resin. The layer containing the specific resin in Example 2 is a black matrix material, that is, polymethyl methacrylate (refractive index 1.50), with respect to the total amount of the layer containing the specific resin, in terms of solid content, contains 15% by mass of The specific resin is a layer with a thickness of 30 μm, that is, silica particles having an average primary particle diameter of 1.5 μm (Seahoster KE-P150 manufactured by NIPPON SHOKUBAI CO., LTD., refractive index 1.43). In the scattering layer of Example 2, the difference in refractive index between the black matrix material and the specific particles was 0.07, and the difference in refractive index was 0.05 or more. In addition, the scattering angle of the scattering layer of Example 2 was 30°, and the diffuse transmittance was 90%. Furthermore, in Example 2, a layer containing a specific resin was formed into a film by spin coating on the surface opposite to the surface on which the chrome pattern (light-shielding pattern) of the exposure mask was formed to form a scattering layer.

In Example 3, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that the dummy support was peeled off, and the exposure mask was brought into contact with the negative photosensitive resin layer for pattern exposure.

In Example 4, a resin pattern and a metal pattern were formed in the same manner as in Example 3 except that the transfer material B was used.

In Example 5, a resin pattern and a metal pattern were formed in the same manner as in Example 1 except that the transfer material C was used.

In Example 6, a resin pattern and a metal pattern were formed in the same manner as in Example 1 except that the transfer material D was used.

In Example 7, as the scattering layer, light up LDS (manufactured by KIMOTO CO., LTD., scattering angle: 30°, light-diffusing polymer film, resin layer having irregularities, thickness 115 μm) was used in the same manner as A resin pattern and a metal pattern were formed in the same manner as in Example 1.

In Example 8, a resin pattern and a metal pattern were formed in the same manner as in Example 1, except that an exposure mask (line/space=5 μm/20 μm, line length 100 μm) was used.

In Example 9, as an exposure mask, the space parts (opening parts) SP of a 3 μm×3 μm square as shown in FIG. In FIG. 7 , only a 3×3 space portion is schematically shown.), and the resin pattern and metal were formed in the same manner as in Example 1, except that the portion other than the space portion was a mask for the light-shielding portion. pattern.

In Comparative Example 1, a resin pattern and a metal pattern were formed in the same manner as in Example 1 except that the scattering layer was not provided.

In Comparative Example 2, a resin pattern and a metal pattern were formed in the same manner as in Example 1 except that the transfer material B was used and the scattering layer was not provided.

【Table 2】 Exposure method scattering layer Types of transfer materials Thickness of negative photosensitive resin layer (μm) Cone Shape Evaluation of Resin Patterns Cone Shape Evaluation of Metal Patterns Exposure margin Example 1 Exposure through dummy support Resin layer with concave and convex A 10 A A A Example 2 Exposure through dummy support layer containing specific particles A 10 B B A Example 3 After peeling off the dummy support, exposure Resin layer with concave and convex A 10 A A A Example 4 After peeling off the dummy support, exposure Resin layer with concave and convex B 10 A A A Example 5 After peeling off the dummy support, exposure Resin layer with concave and convex C 8 B B A Example 6 After peeling off the dummy support, exposure Resin layer with concave and convex D 20 A A A Example 7 After peeling off the dummy support, exposure Resin layer with unevenness*2 A 10 A A A Example 8 After peeling off the dummy support, exposure Resin layer with concave and convex A 10 A A A Example 9 After peeling off the dummy support, exposure Resin layer with concave and convex A 10 A A A Comparative Example 1 Exposure through dummy support none A 10 C C C Comparative Example 2 Exposure through dummy support none B 10 C C C

As shown in the above-mentioned Table 2, the metal pattern formation method of Examples 1-9 was excellent in the tapered shape of the obtained metal pattern compared with the formation method of the metal pattern of Comparative Example 1 or 2.

Regarding the disclosure of Japanese Patent Application No. 2020-130530 filed on July 31, 2020, the entirety of the disclosure is incorporated into this specification by reference. Regarding all documents, patent applications, and technical standards described in this specification, each document, patent application, and technical standards incorporated by reference are incorporated by reference to the same extent as those specifically described and described in each into this manual.

(Symbol Description) 12: Substrate 16: Negative photosensitive resin layer 16A: Patterned hardened layer (resin pattern) 24: Pseudo support 26: Exposure Mask 26A: Shading area of exposure mask 28: Scattering layer 32: Diffuse Exposure Mask 32A: Blocking Area of Diffuse Exposure Mask 100: Laminate 102: Substrate 104: Resin Pattern 104a: negative photosensitive resin layer 106: Metal Pattern θ1: Taper angle of resin pattern θ2: taper angle of metal pattern W1: The width of the top of the resin pattern W2: Width of half the layer thickness of the resin pattern W3: The width of the bottom of the resin pattern W4: Layer thickness of resin pattern W5: The width of the top of the metal pattern W6: Width of half the layer thickness of the metal pattern W7: The width of the bottom of the metal pattern W8: Layer thickness of metal pattern SP: Space Department

FIG. 1 is a schematic diagram showing a preferred example of the method for forming a metal pattern of the present invention. 2 is a schematic cross-sectional view showing a first aspect of an arrangement position of a scattering layer in light irradiation in a pattern exposure step. 3 is a schematic cross-sectional view showing a second aspect of the arrangement position of the scattering layer in the light irradiation in the pattern exposure step. 4 is a schematic cross-sectional view showing an example of an example of a light-scattering exposure mask of a third aspect used as an arrangement position of a scattering layer in light irradiation in a pattern exposure step. 5 is a schematic cross-sectional view showing the position of the length of each part in an example of one resin pattern. 6 is a schematic cross-sectional view showing the position of the length of each part in an example of one metal pattern. FIG. 7 is a schematic diagram showing an example of the pattern shape of the exposure mask.

100: Laminate

102: Substrate

104: Resin Pattern

104a: negative photosensitive resin layer

106: Metal Pattern

θ1: Taper angle of resin pattern

θ2: taper angle of metal pattern

Claims (21)

A method for forming a metal pattern, comprising: the step of preparing a laminate having a negative photosensitive resin layer on a substrate; Light having a component obliquely incident in the thickness direction of the exposure mask is irradiated from the side opposite to the side where the base material is provided in the negative photosensitive resin layer, and the negative photosensitive resin is irradiated with the negative photosensitive resin through the exposure mask. the step of pattern exposure of the layer; a step of developing the negative photosensitive resin layer exposed in the pattern to form a resin pattern having a tapered shape; and A step of forming a metal pattern in a tapered shape corresponding to the shape of the aforementioned resin pattern. The method for forming a metal pattern according to claim 1, wherein In the step of performing the pattern exposure, a scattering layer with a diffuse transmittance of 5% or more and an exposure light source are arranged in this order on the side opposite to the negative photosensitive resin layer side of the exposure mask, and the exposure light source is separated from the exposure light source. The scattering layer is irradiated with scattered light. The method for forming a metal pattern according to claim 2, wherein The scattering layer includes a black matrix material and particles existing in the black matrix material, and the difference in refractive index between the black matrix material and the particles is 0.05 or more. The method for forming a metal pattern according to claim 2 or claim 3, wherein The scattering layer includes a black matrix material and particles present in the black matrix material, and the particles have an average primary particle diameter of 0.3 μm or more. The method for forming a metal pattern according to claim 2, wherein The said scattering layer has unevenness|corrugation on at least one surface. The method for forming a metal pattern according to claim 5, wherein The unevenness has a plurality of convex portions, and the distance between the adjacent convex portions and the tops of the convex portions is 10 μm to 50 μm. The method for forming a metal pattern according to claim 2, wherein The scattering layer and the exposure mask are arranged at positions not in contact with each other. The method for forming a metal pattern according to claim 2, wherein The said scattering layer is in contact with the said exposure mask, and is arrange|positioned on the side opposite to the said negative photosensitive resin layer side in the said exposure mask. The method for forming a metal pattern according to claim 2, wherein The exposure mask is an exposure mask in which the scattering properties of the scattering layer are formed on the surface opposite to the surface on which the light shielding pattern is formed. The method for forming a metal pattern according to claim 1 or claim 2, wherein The steps of the above preparation include using a transfer material having a dummy support and a negative photosensitive resin layer disposed on the dummy support to transfer the negative photosensitive resin layer of the transfer material to the base. The steps of forming the above-mentioned laminated body on the material. The method for forming a metal pattern according to claim 10, wherein The aforementioned pattern exposure in the aforementioned pattern exposure step is a contact exposure in which exposure is performed by bringing the aforementioned dummy support into contact with the aforementioned exposure mask. The method for forming a metal pattern according to claim 10, wherein The pattern exposure in the pattern exposure step is a contact exposure in which the dummy support is peeled off, and then the exposure mask is brought into contact with the laminate having the negative photosensitive resin layer for exposure. The method for forming a metal pattern according to claim 1 or claim 2, wherein The said base material is a conductive base material. The method for forming a metal pattern according to claim 1 or claim 2, wherein The aforementioned metal pattern is a metal pattern formed by an electroplating method. The method for forming a metal pattern according to claim 1 or claim 2, wherein After the step of forming the aforementioned metal pattern, the step of removing the aforementioned resin pattern is further included. The method for forming a metal pattern according to claim 15, wherein Removal of the aforementioned resin pattern is performed by a chemical solution. The method for forming a metal pattern according to claim 1 or claim 2, wherein It further includes the step of removing the aforementioned substrate from the aforementioned metal pattern. The method for forming a metal pattern according to claim 1 or claim 2, wherein The aforementioned resin pattern includes a truncated pyramid shape or a truncated cone shape resin pattern. The method for forming a metal pattern according to claim 1 or claim 2, wherein The thickness of the said negative photosensitive resin layer is 10 micrometers or more. The method for forming a metal pattern according to claim 1 or claim 2, wherein The obtained metal pattern is a metal pattern for metal masks for vapor deposition. A method for manufacturing a metal mask for vapor deposition, comprising the step of forming a metal pattern by using the method for forming a metal pattern according to any one of claim 1 to claim 20.

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